CONTINUOUS FIXED BED CATALYTIC REACTOR AND CATALYTIC REACTION METHOD USING THE SAME

专利摘要:
patent summary of invention: "continuous fixed bed catalytic reactor and catalytic reaction method that uses the same". the present invention relates to a continuous fixed bed catalytic reactor that includes an inflow path for raw gas material for a catalytic reaction and a flow path for reformed gas, a catalytic reaction vessel that is connected to the inflow path and the flow path which holds a clustered catalyst, catalyst seals that have a venting property and retains the clustered catalyst and a drive mechanism that moves the clustered catalyst up and down by moving the catalyst seals up and down low. 21823380v1
公开号:BR112014017557B1
申请号:R112014017557-8
申请日:2013-01-21
公开日:2020-02-18
发明作者:Nobuaki Ito；Kimihito Suzuki；Kenichiro Fujimoto；Kenji Nakao
申请人:Nippon Steel Corporation；
IPC主号:

专利说明:

Invention Patent Descriptive Report for CONTINUOUS FIXED BED CATALYTIC REACTOR AND CATALYTIC REACTION METHOD USING THE SAME.
TECHNICAL FIELD OF THE INVENTION [001] The present invention relates to a continuous fixed bed catalytic reactor to cause a chemical reaction of a fluid with the use of a fibrous catalyst and a set of procedures for a catalytic reaction method using the same.
[002] The priority is claimed in Japanese Patent Application #No. 2012-010460, filed on January 20, 2012, in the Japanese Patent Application No. 2012-010464, filed on January 20, 2012 and Japanese Patent Application #No. 2012-010479, filed on January 20, 2012, the content of which is incorporated by reference in this document.
RELATED TECHNIQUE [003] In a chemical reaction of a fluid using a fixed bed catalytic reaction container filled with a catalyst, in a case where a solid precipitate or the like is generated due to a catalytic reaction, the solid precipitate it often accumulates in spaces between catalyst particles in a catalyst layer. Therefore, a problem with the catalyst layer becoming blocked and consequently unable to ventilate is caused.
[004] For example, Patent Document 1 discloses a set of procedures in which gas containing hydrogen, carbon dioxide, water vapor and tar is brought into contact with a catalyst containing nickel, cerium and aluminum in a fixed bed catalytic reactor, thereby reforming the tar gas. In this set of procedures, solid carbon is precipitated on the surface of the catalyst during reforming and a recycling treatment in which
2/137 water vapor or air is brought into contact with the carbon is required to remove the solid carbon.
[005] In addition, Patent Document 1 also exemplifies the use of a moving bed catalytic reaction container and a fluidized bed catalytic reaction container. In these catalytic reaction vessels, the carbon precipitated on the catalyst surface can be removed during a reaction operation. However, in comparison with the fixed bed catalytic reaction container, the containers described above are complex and the operation is also likely to become unstable in the fluidized bed catalytic reaction container. Therefore, the containers described above are not common as a reaction container particularly for the treatment of a highly corrosive, high pressure and high temperature fluid.
[006] In the fixed bed reaction container that does not have the problem described above the mobile bed catalytic reaction container and the fluidized bed catalyst reaction container, spaces are generally provided on both sides of the catalyst layer, and a fluid is forced to flow from one space to the other space, thereby causing a reaction. To form the spaces on both sides of the catalyst layer, a catalyst retention mechanism is required. A typical example of the catalyst retention mechanism is described in Patent Document 2, and catalyst retention and ventilation are ensured using a metal puncture plate or mesh that has a smaller pore diameter than the catalyst diameter. FIG. 6 illustrates an example thereof, in which a catalyst 2 is accommodated within a catalytic reaction container 1 and the catalyst is retained using a puncture metal plate 3 or a mesh. In FIG. 6, the raw material gas 4 is forced to flow in from an inflow opening 5 and flow out from an outflow opening 6 as reformed gas 7.
3/137 [007] As a method to prevent blockage in the catalyst layer caused by the accumulation of the solid precipitate during the reaction, for example, Patent Document 2 describes a set of procedures that prevent blocking in a second catalyst layer supplementing dust in the gas flowing out from a first layer of catalyst in free spaces through which the gas flows between the two layers of catalyst. However, in this case, it is not possible to prevent blockage in the catalyst layer caused by the dust that is generated in the catalyst layer, which is attached to the catalyst and accumulates therein in the space between the catalyst particles.
[008] Patent Document 3 describes a set of procedures that drain and remove the water generated in a catalyst by radiating an ultrasonic wave to a layer of catalyst in a cell for a fuel battery. However, the ultrasonic wave attenuates significantly in a free space or in a layer of granules and a layer of dust and, therefore, the ultrasonic wave has the capacity to act only in the vicinity of a radiation source. So while this set of procedures is effective for a relatively small catalyst layer like a catalyst layer in a cell for a fuel cell, in a large catalyst layer that treats a large amount of a fluid, it is difficult to vibrate the entire catalyst layer using an ultrasonic wave.
[009] Patent Document 4 describes a set of procedures that suppress coking by performing the hydrocarbon water vapor reforming at a low temperature. However, a catalytic reaction has an optimum reaction temperature condition from the point of view of the catalyst durability and the reaction rate, and the block in the catalyst layer caused by the coke.
4/137 cation occurs under the optimum condition. Therefore, a decrease in the catalytic reaction temperature makes it difficult for the catalytic reaction to occur under the optimum condition and therefore there is a problem of degradation of the catalyst's performance.
[0010] Patent Document 5 describes the removal of partial blockage in a catalyst layer caused by dust accumulated in a moving bed catalytic reaction container using a water hammer or vibrator as a related technique. In this case, there is a problem with the fact that water hammer or vibration increases the filling rate of a catalyst in order to narrow the spaces between the catalyst particles and, in contrast, the fluidity of the catalyst deteriorates.
[0011] Non-Patent Document 1 describes a parallel flow type catalytic reaction container, a monolith type catalytic reaction container, a tube wall type catalytic reaction container and the like as catalytic bed reaction containers fixed specials. All catalytic reaction vessels are equipped with catalyst layers and exclusive air flow paths surrounded by the catalyst layers, thereby reducing the airflow resistance in the catalytic reaction vessels. To briefly describe, in the parallel flow type catalytic reaction container, a plurality of common catalyst layers having both ends retained by a mesh or the like are arranged in parallel and the spaces between the catalyst layers are used as exclusive air flow. In the monolith type catalytic reaction container, a catalyst is carried over the surface of a structure that has a honeycomb structure or the like and the holes in the honeycomb structure are used as exclusive air flow paths. In the tube wall type catalytic reaction container, the tube interiors are used as per
5/137 exclusive air flow strokes and a catalyst is carried by the inner surfaces of the tubes.
[0012] In a case where the exclusive air flow paths are provided, when a solid product is generated from a catalytic reaction, the solid product accumulates on the catalyst surface configuring the exclusive air flow paths so decreasing the flow path width of the exclusive air flow path, and in some cases, the exclusive air flow paths are blocked. Alternatively, even in a case where the air flow paths are not blocked, the exchange of a fluid between the exclusive air flow paths and the catalyst layers is hindered by the solid product accumulated on the catalyst surface configuring the air flow paths. unique airflow and therefore a gas leak phenomenon is caused in which the raw material gas is drained without coming into contact with the active catalyst in order to significantly decrease the efficiency of the catalytic reaction. Alternatively, in a reaction container where a plurality of exclusive air flow paths are provided, the respective exclusive air flow paths are isolated from each other (that is, in a state where the exchange of substance between pathways of adjacent airflow and accompanying heat exchange are suppressed), and airflow paths unable to supply heat from the outside are provided in unique airflow paths located deep inside the reaction container as a reaction reaction container. type of monolith, in the case of an endothermic reaction in which the catalytic reaction is intensive, a reaction on the upper current side significantly decreases the fluid temperature on the downstream side at a temperature where the reaction is not possible, and the reaction efficiency decreases greatly. In contrast, in the case of an exothermic reaction in which the catalytic reaction is intensive, it is not possible
6/137 it is possible to emit the heat generated to the outside through the reaction container in portions deep inside the reaction container and, consequently, the fluid temperature increases excessively on the downstream current side so that the catalyst is inactivated and, in some cases, the catalytic reaction container is burned. [0013] Furthermore, in the case of the monolith type reaction container, it is necessary to mold an entire monolith that is generally complex in shape and large as a carrier to carry the catalyst or a single catalyst structure and, consequently, there is a problem with the fact that the applicable catalyst design (structure) is limited to a relatively simple design (for example, a design in which a catalyst containing a single chemical component is applied uniformly to a carrier surface, or the like) due to the sets of catalyst manufacturing procedures. Therefore, it is significantly difficult to apply the monolith type reaction container to a catalyst that has a complex design (structure) in which the surface is finely divided into a plurality of compartments of different chemical components and the respective chemical components exhibit a catalytic effect. in mutual cooperation as, for example, a tar-reformed catalyst and, even when such application is possible, application becomes extremely expensive.
BACKGROUND DOCUMENT PATENT DOCUMENT [0014] [Patent Document 1] Unexamined Japanese Patent Application, First Publication #No. 2010-77219 [0015] [Patent Document 2] Unexamined Japanese Patent Application, First Publication #No. 2011-6289 [0016] [Patent Document 3] Unexamined Japanese Patent Application, First Publication #No. 2009-48797
7/137 [0017] [Patent Document 4] Unexamined Japanese Patent Application, First Publication #No. 2008-120604 [0018] [Patent Document 5] Unexamined Japanese Patent Application, First Publication #No. H8-24622
DOCUMENT NO PATENT [0019] [Non - Patent Document 1] Catalytic reaction device and its design (2 engineering version) Catalyst Lecture 6 edited by Catalysis Society of Japan and published by Kodansha Ltd. (Tokyo), 1985, pp. 100 to 169
DISCLOSURE OF THE INVENTION
PROBLEMS TO BE SOLVED BY THE INVENTION [0020] As described above, in the related art, there was no method for effectively removing a solid product that is generated and accumulated in a large fixed bed catalyst layer. Therefore, a first objective of the invention is to provide a continuous fixed bed catalytic reactor that has a unit to effectively remove a solid product that is generated and accumulated in a large fixed bed catalyst layer, and a catalytic reaction method in that the crude material gas, particularly the crude material gas containing tar, is highly efficiently reformed with the use of the continuous fixed bed catalytic reactor.
[0021] In addition, there were the following problems with the related technique.
[0022] (A) For punching metal or a mesh, as it is not possible to establish a large orifice ratio (1- [total orifice area] / [apparent cross-sectional area of flow paths]) due to a limitation on the strength of a retention mechanism (a maximum possible orifice ratio is approximately 70%), high airflow resistance or blockage are likely to occur.
[0023] That is, for example, in the case of a retention mechanism
8/137 tion where a mesh is used, there is an upper limit with the mesh size, and consequently it is necessary to decrease the wire diameter of a wire rod that configures the mesh to increase the orifice ratio. However, in a relatively high operating condition required for a catalytic reaction, an extremely thin wire rod is easily broken due to contact with a reactive gas that may be contained in the raw material gas and therefore it is not possible to employ an extremely thin wire rod.
[0024] (B) Since individual orifices are isolated from each other (the entire circumference of a small orifice is surrounded by a solid substance), for example, in the case of a reforming reaction or the like where a catalyst for raw material containing tar is used, in response to a reforming reaction, a solid substance such as the carbon generated on the surface of the catalyst drips and disperses in a retention mechanism, is fixed to the outer circumferential sections of individual holes in the retention, gradually grows towards the center of the hole, finally blocks the holes and disables ventilation.
[0025] Particularly, to retain a highly corrosive or high temperature fluid, although it is desirable to use an alloy containing Ni (stainless steel, INCONEL, HASTELLOY or similar) in terms of strength and resistance to corrosion, metallic Ni often exhibits an action hydrocarbon reforming catalyst to precipitate a solid carbon or similar substance on the surface of a catalyst retainer, and this effect also encourages blockage in the orifices.
[0026] Therefore, a second objective of the invention is to realize a high orifice ratio and the prevention of blockage in catalyst seals, and finally, to reform the tar-containing gas at a high efficiency.
9/137
MEANS TO SOLVE THE PROBLEM [0027] To achieve the objectives described above, the invention uses the following configurations.
[0028] (1) In accordance with a first aspect of the invention, a continuous fixed bed catalytic reactor is provided which includes an inflow path for the raw material gas for a catalytic reaction and an efflux path for the reformed gas; a catalytic reaction container that is connected to the inflow path and the efflux path and retains a fibrous catalyst; a catalyst retainer that has a venting property and retains the fibrous catalyst; and a drive mechanism that moves the fibrous catalyst up and down by moving the catalyst retainer up and down.
[0029] (2) In the continuous fixed bed catalytic reactor according to the above (1), a space to store a liquid or solid foreign substance generated in a catalyst layer can be provided below the catalyst layer which is a collection of the fibrous catalyst particles.
[0030] (3) In the continuous fixed bed catalytic reactor according to the above (1) or (2), at least part of the catalyst particles that configure lateral external circumferential surfaces of the catalyst layer may be in contact with a wall inside the catalytic reaction container.
[0031] (4) In the continuous fixed bed catalytic reactor according to the above (2) or (3), a height of the catalyst layer can be twice or less a thickness of the catalytic reaction container and can be three times or more a maximum value of a typical length of an external surface of the fibrous catalyst.
[0032] (5) In the continuous fixed bed catalytic reactor according to any of the above (1) to (4), an average speed of half
10/137 drive mechanism that moves the catalyst retainer down may be faster than an average speed of the drive mechanism that moves the catalyst retainer up.
[0033] (6) In the continuous fixed bed catalytic reactor according to any of the above (1) to (5), the catalyst retainer can be arranged in parallel with one another, and can have a plurality of pins that directly holds the fibrous catalyst in a front end section.
[0034] (7) In the continuous fixed bed catalytic reactor according to the above (6), a distance between axes between adjacent pins in the plurality of pins can satisfy a condition of [distance between axes between pins] - [dimension of diameter pin external] <[minimum mesh size dimension that allows the fibrous catalyst to pass through].
[0035] (8) In the continuous fixed bed catalytic reactor according to the above (6) or (7), a curvature in a contact section on the pin with the fibrous catalyst may be less than a maximum curvature on a surface of the fibrous catalyst.
[0036] (9) In the continuous fixed bed catalytic reactor according to any of the above (1) to (8), the catalyst retainer may have central rods that form catalyst particle series penetrating a plurality of particles of fibrous catalyst without hindering the mobility of the fibrous catalyst and a retaining plate that sustains the plurality of central rods vertically.
[0037] (10) In the continuous fixed bed catalytic reactor according to the above (9), a material with a high thermal conductivity can be used for the central rods and a heating device can be provided to heat end sections of the central rods.
[0038] (11) In the continuous fixed bed catalytic reactor according to
11/137 above (9) or (10), the drive mechanism can be operated so that a speed of the central rod becomes slower than a speed of the fibrous catalyst particles in a terminal portion of reciprocal movement by the mechanism drive.
[0039] (12) In the continuous fixed bed catalytic reactor according to any of the above (1) to (11), the crude material gas can be the gas containing hydrocarbon and the products of a catalytic reaction can be the solid hydrocarbon and gas or solid carbon.
[0040] (13) In the continuous fixed bed catalytic reactor according to the aforementioned (12), the crude material gas may be the gas containing tar.
[0041] (14) In the continuous fixed bed catalytic reactor according to the above (13), the fibrous catalyst can be a complex oxide containing nickel, magnesium, cerium and aluminum, and is made of a complex oxide that does not contain alumina, in which the complex oxide can be made of crystal phases of NiMgO, MgAl2O4 and CeO2.
[0042] (15) In the continuous fixed bed catalytic reactor as mentioned above (13), the fibrous catalyst can be made of a complex oxide containing nickel, magnesium, cerium, zirconium and aluminum, in which the complex oxide includes crystal phases of NiMgO, MgAl2O4 and CexZ _r1-x O ₂ (0 <x <1).
[0043] (16) In the continuous fixed bed catalytic reactor according to the above (13), the fibrous catalyst can be a catalyst for reforming the tar-containing gas which is a complex oxide represented by aM * bNi * cMg * dO , where a, b and c satisfy a + b + c = 1, 0.02 <a <0.98, 0.01 <b <0.97 and 0.01 <c <0.97, d represents a value in oxygen and a positive element become electrically neutral, M represents at least one element selected at
12/137 from Ti, Zr, Ca, W, Mn, Zn, Sr, Ba, Ta, Co, Mo, Re, platinum, rhenium, palladium, rhodium, Li, Na, K, Fe, Cu, Cr, La , Pr and Nd, at least one oxide selected from silica, alumina and zeolite is triggered to the complex oxide, and an amount of the oxide selected from silica, alumina and zeolite is in a range of 1% by mass at 90% in mass in relation to the complex oxide.
[0044] (17) In accordance with a second aspect of the invention, a continuous fixed bed catalytic reaction method is provided in which a catalytic reaction is caused using the continuous fixed bed catalytic reactor according to any of the above (1) to (16). EFFECTS OF THE INVENTION [0045] According to the continuous fixed bed catalytic reactor of the invention, it is possible to effectively remove a solid accumulated substance which is generated and accumulated in the catalyst particles in the fixed bed catalyst layer in order to degrade the catalyst performance and cause blockage in the catalyst layer by moving the entire catalyst layer up and down. Therefore, it is not necessary to stop the operation to wash the blocked catalyst retainer as in the related technique, and it is possible to operate the reactor continuously. In addition, it is possible to cause with a high efficiency a catalytic reaction that generates a solid product such as solid carbon with the use of the continuous fixed bed catalytic reactor.
BRIEF DESCRIPTION OF THE DRAWINGS [0046] FIG. 1A is a plan view of a continuous fixed bed catalytic reactor according to a first embodiment of the invention.
[0047] FIG. 1B is a front view of the continuous fixed bed catalytic reactor according to the first embodiment of the invention.
[0048] FIG. 1C is a side view of the continuous fixed bed catalytic reactor according to the first embodiment of the invention.
13/137 [0049] FIG. 2A is a plan view of a continuous fixed bed catalytic reactor according to a second embodiment of the invention.
[0050] FIG. 2B is a front view of the continuous fixed bed catalytic reactor according to the second embodiment of the invention.
[0051] FIG. 2C is a side view of the continuous fixed bed catalytic reactor according to the second embodiment of the invention.
[0052] FIG. 3A is a plan view of a continuous fixed bed catalytic reactor according to a third embodiment of the invention.
[0053] FIG. 3B is a front view of the continuous fixed bed catalytic reactor according to the third embodiment of the invention.
[0054] FIG. 3C is a side view of the continuous fixed bed catalytic reactor according to the third embodiment of the invention.
[0055] FIG. 4 is a graph illustrating a relationship between an aspect ratio of a catalyst layer and a height of a top end of the catalyst layer.
[0056] FIG. 5 is a graph illustrating a relationship between an aspect ratio of the catalyst layer and a standard peak / peak charge.
[0057] FIG. 6 is a schematic view depicting a catalytic reaction container of the related technique.
[0058] FIG. 7 is a schematic view of a retainer used in the continuous fixed bed catalytic reactor according to the second embodiment of the invention.
[0059] FIG. 8A is a plan view of a continuous fixed bed catalytic reactor according to a fourth embodiment of the invention.
[0060] FIG. 8B is a front view of the continuous fixed bed catalytic reactor according to the fourth embodiment of the invention.
[0061] FIG. 8C is a side view of the continuous fixed bed catalytic reactor according to the fourth embodiment of the invention.
[0062] FIG. 8D is an enlarged cross-sectional view obtained
14/137 along line X-X in FIG. 8B.
[0063] FIG. 9 is a schematic view of a retainer used in the continuous fixed bed catalytic reactor according to the fourth embodiment of the invention.
[0064] FIG. 10 is a view illustrating a pin arrangement on the retainer.
[0065] FIG. 11 is a schematic view illustrating an example of modification of the catalyst retainer.
[0066] FIG. 12 is a schematic view of a continuous fixed bed catalytic reactor according to a fifth embodiment of the invention.
[0067] FIG. 13A is a cross-sectional view A-A of a continuous fixed bed catalytic reactor according to a sixth embodiment of the invention.
[0068] FIG. 13B is a cross-sectional view of a front surface of the continuous fixed bed catalytic reactor according to the sixth embodiment of the invention.
[0069] FIG. 13C is a cross-sectional view B-B of the continuous fixed bed catalytic reactor according to the sixth embodiment of the invention.
[0070] FIG. 14A is a cross-sectional view of a continuous fixed bed catalytic reactor according to an example of modification of the sixth embodiment of the invention.
[0071] FIG. 14B is a cross-sectional view of a front surface of the continuous fixed bed catalytic reactor according to the modification example of the sixth embodiment of the invention.
[0072] FIG. 14C is a cross-sectional view of the continuous fixed bed catalytic reactor according to the modification example of the sixth embodiment of the invention.
[0073] FIG. 15A is a plan view of a catalytic bed reactor
15/137 continuous fixed according to a seventh embodiment of the invention. [0074] FIG. 15B is a front view of the continuous fixed bed catalytic reactor according to the seventh embodiment of the invention.
[0075] FIG. 15C is a side view of the continuous fixed bed catalytic reactor according to the seventh embodiment of the invention.
[0076] FIG. 16A is a plan view of a continuous fixed bed catalytic reactor according to an eighth embodiment of the invention.
[0077] FIG. 16B is a front view of the continuous fixed bed catalytic reactor according to the eighth embodiment of the invention.
[0078] FIG. 16C is a side view of the continuous fixed bed catalytic reactor according to the eighth embodiment of the invention.
[0079] FIG. 17 is a schematic view of a continuous fixed bed catalytic reactor according to a ninth embodiment of the invention.
[0080] FIG. 18 is a graph illustrating test results from Example 3-1.
[0081] FIG. 19A is a plan view to describe a series catalyst.
[0082] FIG. 19B is a side view to describe the catalyst in series.
[0083] FIG. 20A is a plan view to describe a catalyst fence.
[0084] FIG. 20B is a side view to describe the series fence.
[0085] FIG. 21 is a graph illustrating test results from Example 3-2.
MODALITIES OF THE INVENTION [0086] As a result of the investigations, the present inventors observed that a mechanism of the accumulation of solid carbon generated between the catalyst particles in a catalyst layer of
16/137 fixed bed was as described below.
[0087] (1) In spaces between catalysts formed between a plurality of adjacent catalyst particles in a fixed bed catalyst layer, (partially reformed) the raw material gas flows in through voids on the upper current side of the chain main, and the reformed gas (including part of the unreformed raw material gas) flows out through the voids on the current side downstream of the main stream as reformed gas.
[0088] (2) When the raw material gas supplied to the spaces between the catalyst is reformed by a catalytic reaction, part of the solid carbon generated on the surface of the catalyst is fixed to the surface of the catalyst.
[0089] (3) When the crude material gas supplied to the spaces between catalyst is reformed by a catalytic reaction, fine particles of solid carbon that were generated on the surface of the catalyst and then released from the surface of the catalyst by an air current are attached to the solid carbon that was previously attached to the catalyst surface, whereby carbon spheres that have a diameter in the range of several tens of micrometers to approximately one millimeter grow on the surface of the catalyst.
[0090] (4) The carbon spheres are occasionally released from the surface of the catalyst, and are re-fixed to other previously existing carbon spheres, through which a layer of solid carbon accumulation that consists of multiple layers of carbon spheres and has a thickness that reaches up to several millimeters is formed on the surface of the catalyst.
[0091] (5) The accumulation layer of solid carbon is substantially porous and therefore a large pressure loss is caused when the gas is vented at a high speed.
[0092] (6) When the resistance to ventilation becomes excessive
17/137 in spaces between specific catalysts, the main current flows preferentially through spaces between the catalyst that has a lower ventilation resistance. However, since the solid carbon build-up layer is porous, even in spaces that have an excessively increased resistance to ventilation due to the build-up of solid carbon, the gas flow in the spaces between catalyst is not completely blocked, and the raw material gas it is continuously supplied to the catalyst surface at a low flow rate. As a result, the growth of solid carbon on the catalyst surface by gas reforming progresses continuously all the time (however, since the area exposed on the catalyst surface decreases, the rate of reforming decreases significantly compared to the rate of reforming in the initial stage ).
[0093] (7) When solid carbon accumulates in most of the spaces between the catalyst in the catalyst layer, the pressure loss becomes excessive as a whole in the catalyst layer, and a blocked state is caused (in a container of catalytic reaction, the raw material gas needs to be treated at a predetermined flow rate and, in a state where the pressure loss inevitably exceeds the allowable value (determined by the gas carrying capacity, the strength of the container, and the like) of a reactor although the raw material gas is vented through all spaces between the catalyst at the predetermined flow rate, the catalyst layer becomes substantially blocked).
[0094] When the layer of solid carbon accumulation is removed exclusively from the catalyst surface in the fixed bed catalytic reaction container in which a reforming reaction of hydrogen, carbon dioxide, water vapor and tar-containing gas is caused and the catalyst layer is blocked, the accumulation layer of solid carbon is placed in a container, and a mechanical force
18/137 external only as light vibration is applied, the layer of accumulation of solid carbon is easily separated at the limits of the carbon spheres that are configuration units, and is pulverized. To remove the solid carbon from the catalyst layer blocked by the accumulation written above the solid carbon, the inventors tested a variety of measures.
[0095] The inventors tested backwashing the catalyst layer by blowing from the outside of the catalyst layer as a first measure. In detail, the backwash of the catalyst layer was tested by supplying a nitrogen gas supply tube on the current side downstream of the catalyst layer in the reaction container and spraying a high speed nitrogen stream onto the catalyst layer. Backwashing is a common method used as a measure to resolve the blockage in a dust removal filter.
[0096] The result was that while part of the solid carbon was removed, the pressure loss in the catalyst layer changed only slightly, and there was no effect to resolve the block. The reasons for the result described above are considered as follows.
[0097] 1) In the case of a filter, between dust grains that flow into the filter from the upper current side, dust grains larger than the filter mesh size are stuck in place. Generally, the filter has a larger mesh size on the upper chain side and therefore in a case where backwashing is performed by supplying a high speed flow to a blocked part of the filter from the downstream side of the main stream, between the trapped dust grains, the dust grains released from the filter meshes pass through large meshes as they are transported by the high speed airflow towards the upper stream side of the stream
19/137 and therefore the dust grains are not susceptible to being trapped in the meshes and can be escaped outside the filter. [0098] However, the accumulation layer of solid carbon or the like that is a by-product of the catalytic reaction is generated in the spaces between catalyst with the use of gas as a raw material instead of flowing inward from the upper current side of the main current. Therefore, the sizes of the accumulated carbon particles are not always smaller than the inflow and outflow voids in the spaces between the catalyst and, therefore, a large number of accumulated carbon particles that cannot flow out from the spaces between the catalyst. catalyst remains in the spaces between the catalyst.
[0099] When the carbon accumulation layer is broken and pulverized, it may be possible to flow the accumulated carbon particles out of the spaces between the catalyst. However, generally, the stress supplied by the air flow to the accumulated carbon is small (even when a large air pressure difference is supplied to the entire catalyst layer, since it is common for the catalyst to be loaded onto the catalyst layer in multiple layers, the difference in air pressure between the inlet and outlet of each space between the catalyst becomes small, and it is not possible to supply a large stress to the accumulated carbon), and it is not possible to break the accumulated carbon layer.
[00100] 2) When part of the carbon is removed, the narrow flow paths formed by a series of a small number of spaces between the catalyst whose air flow resistance has been decreased as a result of the carbon removal are newly formed in the layer of catalyst, and most of the main current flows mainly through these flow paths. At that point, a current of air rarely crosses the spaces between the catalyst other than
20/137 newly formed flow paths and therefore carbon is no longer removed. Therefore, the flow velocity increases in the narrow flow paths through which the main current passes, and a large pressure loss is caused and, therefore, the blocked state does not improve. Since the new flow paths formed as described above are also quickly blocked again by the generation and accumulation of new carbon in the flow paths, the backwash effect lasts only for a short period of time. However, in the spaces between the catalyst, made (surrounded by) the inactivated catalyst at an early stage, the reblocking of the spaces between the catalyst as described above does not occur. However, when the main current comes into contact only with the inactivated catalyst and passes through the catalyst layer, it is not possible to reform the gas and, therefore, the filter is not capable of exhibiting performances like the catalytic reaction container.
[00101] Based on the above, the following conclusion can be drawn.
[00102] That is, usually, in the blocked catalyst layer, a state of [00103] [the size of each accumulated carbon]> [the void in the space between the catalyst] [00104] is formed, and it is not possible to remove one large amount of carbon from the catalyst layer unless [00105] [the size of each accumulated carbon] <[the void in the space between catalyst] [00106] is satisfied, and the backwash of the catalyst layer by blowing from the outside of the catalyst layer is not effective for removing carbon.
[00107] Therefore, as a second measure, an attempt was made to break the accumulated carbon layer or to enlarge the es
21/137 space between catalyst by water hammer on the outer surface of the reaction container.
[00108] The result is as follows: when the (first water hammer) was performed after the initial blockage occurred, part of the accumulated carbon can be removed, the pressure loss was also reduced by approximately half, and a certain effect was observed. After that, when the water hammer (second water hammer) was performed again after the blocking recurrence, only a small amount of accumulated carbon was removed, the pressure loss was not changed, and it was not possible to avoid the blockage. That is, it was observed that the second and last water hammer on the outer surface of the reaction container were not effective for removing accumulated carbon. The reason for the result described above is considered as follows.
[00109] 1) When the catalyst is accumulated in the reaction container, it is common to simply drop the catalyst from above and, therefore, the catalyst is not in a closed packaged state in the catalyst layer. When the first water hammer is performed on the catalyst not in a closed packaged state, the catalyst transforms into a closed packaged state or an almost compact closed state due to vibration (for simplification, hereinafter referred to as closed packaged emphasis). During the closed packaging process, the relative position between catalyst particles moves a total of approximately 30% of the typical length of the catalyst particles. During the movement described above from the relative position (ie movement between relative catalyst), since part of the accumulated carbon is broken down due to contact stress with the catalyst in order to be reduced in size, and there are times when the intervals between catalyst temporarily expand, a ratio of the
22/137 [00110] [size of each accumulated carbon] <[of the void in the space between catalyst] [00111] is carried out, the catalyst drips on the catalyst layer, and finally, it is removed from the catalyst layer.
[00112] 2) However, since the catalyst layer is packaged closed after the end of the first water hammer, even when the second and last water hammer are performed, the relative positions of the catalyst particles rarely change, and the disruption of the accumulated carbon or widening of the intervals between the catalyst particles does not occur. Therefore, in the second and last water hammer, an effect that removes the accumulated carbon was not observed.
[00113] Based on the above, the following conclusion can be drawn.
[00114] That is, in many cases, since the blocking solution effect of the first water hammer does not last for the duration of treatment required in the catalytic reaction container, the water hammer on the outer surface of the reaction container is not sufficient for the continuous removal of accumulated carbon. To continuously remove the accumulated carbon from the catalyst layer, a method of defining [00115] [the size of each accumulated carbon] <[the void in the space between catalyst], [00116] and then breaking the closed packaged state of the catalyst is required.
[00117] Based on the described conclusion, the movement of the catalyst layer in the reaction container was tested as a third measure. In more detail, the up and down movement of the entire catalyst layer was tested by moving up and down a retainer provided at the bottom of the catalyst layer in one
23/137 state in which the catalyst was in contact with the internal wall of the reaction container in an immobile reaction container (that is, a state in which at least part of the catalyst particles that configure the lateral outer circumferential surfaces of the catalyst was in contact with the inner wall of the catalytic reaction container). As a result, the up and down movement of the catalyst layer reaches a stable state (on average, the catalyst layer returns to the initial state after an up and down cycle of operation) after several times of the up and down operation. down. When the retainer is moved upward in the steady state, generally the amount of lift from the top end of the catalyst layer is less than the amount of lift from the bottom end of the catalyst layer, and the top and bottom ends of the catalyst layer return to the initial locations after the retainer is moved down. Therefore, in the up and down cycle of the retainer, the average packaging ratio of the catalyst layer changes (the average packaging ratio of the catalyst layer increases when the retainer is moved upwards, and the average packaging ratio of the layer catalyst decreases when the retainer is moved down), and the movement between relative catalyst occurs in the catalyst layer at least in an up and down direction. The difference in the amount of elevation between the top end and bottom end of the catalyst layer during the up and down movement of the retainer increases as the height of the catalyst layer (the distance between the top end and the bottom end of the catalyst layer) increases, and in the end, the top end of the catalyst layer is rarely moved upwards. In a state where the top end of the catalyst layer is not moved, since the catalyst particles in the vicinity of the end
24/137 top density of the catalyst layer is not moved by the up and down movement of the retainer, the movement between the relative catalyst is not caused. As a result, in this region, it is not possible to remove the carbon accumulated between the catalyst particles by moving the retainer up and down. Therefore, it has been observed that, to remove the carbon accumulated between the catalyst particles in the entire catalyst layer by moving the retainer up and down, it is necessary not only to change the average packaging ratio of the catalyst layer, but also to ensure a sufficient up and down stroke even at the top end of the catalyst layer by moving the retainer up and down.
[00118] FIG. 4 illustrates the height of the top end of the catalyst layer expressed as the displacement of the height of the top end of the catalyst layer in a steady state after the catalyst layer in the immobile reaction container is moved up and down five times in a state in which the catalyst is in contact with the inner wall of the reaction container by moving the retainer upwards as high as 27 mm in an apparatus that has a mechanism in which the catalyst layer is formed by loading the catalyst into a container duct-shaped reaction plate that has a rectangular cross-sectional surface with a constant cross-sectional area and the catalyst layer is retained by providing the retainer below the catalyst layer. The vertical geometric axis indicates the height of the top end of the catalyst layer, and the criterion height of 0 mm corresponds to the location of the top end of the catalyst layer in the vertical direction before the retainer is moved upwards. The height of the catalyst layer / thickness of the reaction container on the horizontal geometric axis refers to an index which will henceforth also be called ra
25/137 aspect ratio of the catalyst layer, and the reaction container thickness corresponds to the shortest length of typical reaction container lengths in a horizontal plane, for example, the length of the short side in a case where the cut horizontal cross-section of the reaction container is rectangular, and the diameter in a case where the horizontal cross-section of the reaction container is round.
[00119] From FIG. 4, it is observed that when the aspect ratio (catalyst layer height / reaction container thickness) of the catalyst layer is greater than two, the amount of elevation of the catalyst layer (the amount of elevation based on the height before starting the up and down movement which is finally admitted after five times of the up and down operation) is much less than the amount of lift of the retainer (27 mm) or the external size (diameter) of the catalyst (15 mm). This indicates that when the retainer is moved upwards (when the catalyst layer is moved upwards), the catalyst packing ratio increases and when the retainer is moved downwards (when the catalyst layer is moved downwards) , the packaging ratio decreases. Since the catalyst on the bottom side has a higher movement speed during the up and down movement of the retainer, the movement speeds of the respective catalyst particles differ in the height direction of the catalyst layer, and the movement between relative catalyst it is caused at least in the vertical direction. Under the condition described above (the aspect ratio> 2), the elevation amplitude of the top end section of the catalyst layer is small and therefore the relative movement between the catalyst particles is relatively small in that section, and the escape capacity of the carbon accumulated between the catalyst particles is low.
26/137 [00120] Conversely, when the aspect ratio of the catalyst layer is equal to or less than two (aspect ratio = 1.8), it is observed that the amount of elevation of the top edge of the layer of catalyst is slightly less than the lift amount of the retainer (the top end of the catalyst layer is moved up as high as 20 mm and compared to the lift amount of the 27 mm retainer). That is, under the condition described above, the same level of the up and down stroke as in the retainer is also satisfied at the top end of the catalyst layer, the movement between relative catalyst and the entire area of the catalyst layer which means that a change in the packing ratio of the catalyst layer by the up and down movement of the retainer is guaranteed can be made, and the escape capacity of the accumulated carbon between the catalyst particles is high.
[00121] Furthermore, in addition to the effect described above of the movement between relative catalyst in the vertical direction, when the catalyst layer is moved up and down in a state where the catalyst is in contact with the inner wall of the reaction container , it is possible to exhibit an effect that generates movement between relative catalyst in the thickness direction and in the width direction of the catalyst layer as well. That is, when the change in the relative position between the catalyst particles during the change in the packing ratio caused by the up and down movement of the catalyst layer is considered, the state of restriction in relation to the movement of the respective catalyst particles in the thickness direction of the catalyst layer (the same as the thickness direction of the reaction container) differs. This results from the restriction in relation to the catalyst particles in the vicinity of the wall surface increased by friction with the wall surface and velocities.
27/137 small up and down movement in the initial phase. As a result, the movement speeds of the respective catalyst particles in the thickness direction of the catalyst layer differ, and therefore the relative movement between the catalyst particles is caused.
[00122] In a case where the catalyst layer is moved up and down by placing the catalyst in contact with the inner wall of the container in the reaction container as described above, the change in the relative position between the catalyst particles during the change in the packing ratio caused by the up and down movement of the catalyst layer it becomes large; for example, in a case where the up and down stroke of the retainer is 30 mm, the change in relative position between the catalyst particles reaches approximately 30% of the typical length (for example, 15 mm) of the catalyst particles each time the catalyst layer is moved up and down.
[00123] It has been observed that when the catalyst is placed in contact with the inner wall of the container in the reaction container, and the catalyst layer is moved up and down, thereby moving the individual relative positions between the catalyst particles and by stirring the entire catalyst layer as described above, it is possible to remove a solid substance accumulated between the catalyst particles along the entire catalyst layer, for example, carbon or similar accumulated during the gas reforming reaction that it contains a tar component of the catalyst layer, effectively dripping the solid substance between the catalyst particles.
[00124] Regarding the up and down speed of the catalyst, the average lowering speed is preferably higher than the average lifting speed. Particularly, when the
The retainer is lowered at a speed greater than the free fall speed of the bottom part of the catalyst layer, more preferably, at a speed greater than the free fall speed of the catalyst at the bottom end of the catalyst layer. , since the bottom end of the catalyst layer is separated from the retainer, and the catalyst particles are gradually accumulated in the retainer that was stopped in advance at the location of the bottom end of the retainer, it is possible to make the packaged catalyst layer closed packaged loosely through the redisposition of the catalyst particles. At the same time, since there may be a time when the gaps between the catalyst particles become extremely large during the dripping of the catalyst particles, it is possible to effectively remove the solid substance accumulated between the catalyst particles.
[00125] On the contrary, in a case where the retainer and reaction container are moved up and down at a constant speed, since the entire catalyst layer is moved up and down at the same speed as those for the retainer and the reaction container, there is no relative movement between the catalyst particles. Therefore, the effect to remove solid carbon or the like on the catalyst surface is low (the same effect as the water hammer from the outside of the reaction container). In addition, the same result is also achieved in a case where the entire catalyst is placed in a basket or the like, and the basket and the catalyst layer are moved up and down at the same time.
[00126] Based on what was described above, it was observed that, to remove an accumulated solid generated and accumulated in the catalyst in the fixed bed catalyst layer, it is preferable to move relatively the catalyst layer in relation to the reaction container along with the retainer. This is the basic principle of the present modality.
29/137
In addition, according to the embodiment, when the entire catalyst layer is stirred (the relative positions of the respective catalyst particles are moved) for a short time during the catalyst reaction from which a solid product such as carbon solid is generated, there is an excellent effect that the solid product accumulated between the catalyst particles is effectively dripped between the catalyst particles along the entire catalyst layer, whereby the solid product can be removed from the catalyst layer catalyst. The solid product removed from the catalyst layer can be dripped through a retainer opening section, and the solid product remaining in the bottom section after dripping can be escaped to the outside of the system during, for example, exchange or the like. catalyst.
[00127] The modality can be applied preferentially for the removal of the solid product generated and accumulated in the catalyst in the fixed bed catalyst layer. For example, in the tar-containing gas reforming reaction where a complex metal oxide catalyst containing nickel, magnesium, cerium, zirconium and aluminum is used, compared to other reactions, a greater amount of solid carbon is accumulated in the catalyst surface, and the need for removing solid carbon is also stronger. According to the modality, even in a case where a catalyst for the tar reforming gas reaction where a larger amount of solid carbon is accumulated on the catalyst surface compared to other reactions as described above, makes it it is possible to effectively remove the solid product generated and accumulated in the catalyst.
[00128] Unlike a fixed catalyst bed that is the subject of the modality, in a moving bed, it is a principle to continuously move (and shake) the catalyst during the reaction. On the contrary, in the modalida
30/137 de, since the catalyst layer needs to be moved intermittently for a short period of time in the reaction container, it is not necessary to stir the catalyst during the reaction. In addition, in the moving bed, a constant amount of the catalyst is escaped to the outside of the system during the reaction, and the same amount of the catalyst is supplied from the outside of the system. On the contrary, in the modality, the catalyst is not changed during the reaction (since the catalyst layer is a fixed bed).
[00129] Furthermore, as a fourth measure, it has been tested that, with the use of a series of catalyst particles defined as a plurality of catalyst particles that have a through hole in it that is connected with the use of a rod central and which is arranged in a row, a catalyst bar which is a part defined as a plurality of the catalyst particle series arranged at certain intervals is arranged in a catalytic reaction container, the spaces between the respective catalyst particle series they are used as exclusive air flow paths, and the catalyst bar is moved reciprocally for a short period of time after a certain period of time has elapsed since the start of operation of a catalytic reactor. As a result, the following was observed:
[00130] (a) Over a period of time from the initial state of the reaction to the accumulation of a predetermined amount of a solid reaction product on the catalyst surface, [00131] [the size of each accumulated carbon] <[the void in space between catalyst (the width of the exclusive air flow path)] [00132] is performed. Therefore, the accumulated substance can be separated from the surface of the catalyst by moving the catalyst bar reciprocally until a predetermined amount of the solid product is accumulated in the catalyst. In addition, when the product only
31/137 separate lipid is dripped or transported by air flow through the exclusive air flow paths, the solid product can be escaped outside the catalytic reaction container. Since it is possible to return the product accumulation state on the catalyst surface to the same state as the initial reaction state by removing the product on the catalyst surface in the manner described above, the ventilation property of the reaction container can be maintained favorable at all times by repeating the reciprocal movement operation described above each time the time of product accumulation progresses.
[00133] Here, according to the modality, it is possible to enlarge the cross section of each exclusive air flow path (for example, at the same level as the catalyst container height in the main current direction and the cross section area of the catalyst in a direction perpendicular to the main current direction) while maintaining the same level of the catalyst packaging ratio as in the catalyst layer which has a simple laminated structure of the related technique. Therefore, the product accumulated in a small amount in the air flow paths does not hamper the ventilation property of the reaction container and, therefore, it is possible to decrease the frequency required for the reciprocal action described above (for example, once an hour) . This results from the fact that, in the embodiment, the voids between the catalyst particles that were a number of small spaces dispersed between the individual catalyst particles in the related art catalyst layer that has a simple laminate structure are concentrated in a small number large airflow paths, whereby both a high ventilation property and a high packaging ratio can be satisfied. On the other hand, the related technique catalyst layer which has a simple laminated structure
32/137 has a structure in which individual catalyst particles support each other in order to form and retain the catalyst layer and therefore the air flow paths formed between adjacent catalyst particles are divided into fine segments for the particles catalyst, and are susceptible to forming narrow parts. In the catalyst layer described above, the cross-sectional area of the flow path that can be guaranteed in the narrow parts of the airflow path is approximately 1/10 of the cross-sectional area of the catalyst and therefore the resistance to ventilation of the reaction container is increased abruptly even when a small amount of a product is accumulated in the air flow paths (the ventilation resistance of the air flow path is generally dependent on the cross sectional area of the narrow part). In addition, in addition to the catalyst layer described above, in another catalyst layer of the related technique, since a product was accumulated in the air flow paths, since there was no method for removing the accumulated product, in a container of reaction in which a product was highly susceptible to being generated by a reaction, the continuous useful time was extremely short due to a limitation caused by an increase in resistance to ventilation.
[00134] (b) During the reciprocal movement of the catalyst bar, since the adjacent catalyst particles are not coupled with each other in the respective catalyst particle series, the relative movement is highly susceptible to occur between the catalyst particles (for example, since the frictional force between the inner catalyst wall and the surface of a central stem adjacent to the inner catalyst wall differs depending on the catalyst, the speeds of the respective catalyst particles driven by the central stem vary even when the stem central is moved
33/137 at a constant speed). Therefore, the catalyst particles easily collide with each other, and strong surface vibrations occur between the catalyst particles during the collision, whereby it is possible to separate the product from the catalyst surface. [00135] Conversely, in the case of a related technique tube wall type catalytic reaction container in which the tube interiors are used as the exclusive air flow paths, and a catalyst is loaded by the inner surfaces of the tubes , since the catalyst carrier is a unique structure, even when the catalyst carrier is moved reciprocally, the catalyst carrier is moved simply as a whole, and there is no relative movement in the carrier. Therefore, the catalyst surface vibration has only a limited effect (for example, even when an impact is partially supplied, the vibration on the catalyst surface is abruptly attenuated as it moves away from the impact point. In addition, even when the entire tube wall is impacted uniformly, the mechanism becomes excessively complex in terms of structure, which is not preferred), the effect to separate the product from the catalyst surface is small. In a reaction container equipped with other exclusive air flow paths (for example, a monolith type reaction container) also, since the catalyst structure is a unique structure, it is difficult to effectively vibrate the entire catalyst through same reason as in the tube wall type reaction container.
[00136] (c) Since the periodic reciprocal movement of the catalyst bar decreases the accumulation of a mass-shaped product on the catalyst surface, the raw material gas can reach the catalyst surface at all times in the catalyst container reaction. Therefore, the efficiency of the catalytic reaction decreases only slightly.
34/137 [00137] (d) Since the exclusive air flow paths between the catalyst particle series are coupled with each other, the gas is susceptible to diffuse (substance exchange and accompanying heat exchange) in a direction perpendicular to the main stream of a fluid. Therefore, a sufficient amount of heat can be supplied from a heated surface to the catalyst present away from the outer wall surface of the catalytic reaction container which is the heated surface (in a case where the catalytic reaction is an endothermic reaction) through diffusion of gas, and gas leakage does not occur easily.
[00138] (e) Particularly, since a highly thermally conductive material is used for the central rod for the catalyst particle series, and the end sections of the central rod are heated, the heat absorption by the reaction is compensated by heating if the catalyst present distant from the wall surface through the central geometric axis, whereby a decrease in the catalyst temperature and a decrease in the reforming efficiency caused by the decrease in the catalyst temperature can be avoided and therefore it is possible to prevent further the occurrence of gas leak.
[00139] When a plurality of catalyst particle series in which individual catalyst particles are connected using the central rod and are arranged in a row is used, the spaces between the respective catalyst particle series are used as the paths of unique airflow, and the catalyst bar which is a collection of the catalyst particle series is moved reciprocally in the catalytic reaction container, it is possible to exhibit an excellent effect that a solid product accumulated on the catalyst surface across the area of the catalyst layer (the entire catalyst bar) is dripped effectively, and is removed from the catalyst layer (the catalyst bar).
35/137 [00140] Therefore, the modality can be applied preferentially for the removal of the solid product generated and accumulated in the catalyst in the fixed bed catalyst layer. For example, in the tar-containing gas reforming reaction where a complex metal oxide catalyst containing nickel, magnesium, cerium, zirconium and aluminum is used, compared to other reactions, a greater amount of solid carbon is accumulated in the catalyst surface, and the need for removing solid carbon is also stronger. According to the modality, even in a case where a catalyst for the tar reforming gas reaction where a larger amount of solid carbon is accumulated on the surface of the catalyst compared to other reactions as described above, makes it it is possible to effectively remove the solid product generated and accumulated in the catalyst.
[00141] Unlike a fixed catalyst bed, in a moving bed, it is a principle to continuously move (and shake) the catalyst during a reaction. On the contrary, in the embodiment, since the catalyst layer needs to be moved intermittently for a short period of time in the reaction container, it is not necessary to stir the catalyst during a reaction. In addition, in the moving bed, a constant amount of the catalyst is escaped out of the system during a reaction, and the same amount of the catalyst is supplied from outside the system. On the contrary, in the modality, the catalyst is not changed during a reaction (since the catalyst layer is a fixed bed).
First to third embodiments [00142] The first to third embodiments of the invention will be described in detail with reference to the accompanying drawings. However, in the following drawings and description, components that have substantially the same function will be provided with the same
36/137 reference, and the description of a duplicate will not be made. First modality
Global Structure [00143] FIGS. 1A, 1B and 1C illustrate a continuous fixed bed catalytic reactor 110 according to a first embodiment of the invention. FIG. 1A is a plan view, FIG. 1B is a front view and FIG. 1C is a side view. The continuous fixed bed catalytic reactor 110 of the embodiment includes a reaction container 111. The reaction container 111 accommodates a layer of catalyst 113 which is a group of fibrous catalyst particles and is supported by a retainer 112 which has a ventilation property in the bottom section. Among the catalyst particles in the catalyst layer 113, the catalyst particles adjacent to the inner wall of the reaction container (not shown) are in contact with the inner wall of the reaction container. In the embodiment, since the catalyst layer is moved up and down by placing the catalyst particles in contact with the inner wall of the reaction container, the inner surface of the reaction container 111 is preferably flat in order to prevent the impediment of the catalyst movement during the up and down movement. A drive mechanism 120 for moving the catalyst layer 113 up and down by moving the retainer up and down is located below the retainer 112, and the drive mechanism 120 is configured from an up and down motion apparatus. down 121 and a driving geometry axis 122 connecting the up and down movement apparatus 121 to retainer 112.
[00144] In reaction container 111, raw material gas 114 is supplied from the bottom section and is reacted in the catalyst layer 113, and the reformed gas 115 from the catalyst layer 113 is escaped through the top section of the catalyst container. reaction 111. Examples of
37/137 raw material 114 includes hydrocarbon containing gas, hydrocarbon and tar containing gas, and the like. Examples of the reformed gas 115 include the reformed gas obtained by reforming the hydrocarbon-containing gas. Examples of the catalyst include a fibrous catalyst for the reforming of hydrocarbons and the like, and a solid substance, for example, solid carbon or the like is accumulated on the surface of the catalyst as a by-product of the catalytic reaction. In a case where the catalytic reaction is an endothermic reaction, the temperature and heat required for the reaction can be supplied by placing the catalytic reaction container 111, for example, in a heating furnace (not shown). In a case where the catalytic reaction is an exothermic reaction, the reaction heat can be removed by making a refrigerant flow through a refrigerant flow path (not shown) provided outside the catalytic reaction container. Depending on the cases, the raw material gas can be supplied to the reaction container 111 in order to flow from the top side to the bottom side of the catalyst layer 113 which is opposite to the flow in FIGS. 1A, 1B and 1C.
Reaction container format [00145] Reaction container 111 can have any shape as long as the reaction container has openings 116a and 117a and is capable of storing the catalyst in a space between the openings. The opening 116a communicates with a supply tube that sets up an inflow path 116 for a catalytic reaction fluid (crude gas), and is equivalent to an inflow opening for the reaction container 111 for the crude gas for the catalytic reaction. The opening 117a communicates with an exhaust pipe that sets up an efflux path 117 for the reformed gas from the reaction container 111, and is equivalent to an efflux opening of the reaction container 111 for the reformed gas. Reaction container 111
38/137 may have, for example, a cylindrical shape, a rectangular duct shape or the like, and hereinafter, a rectangular duct shaped reaction container will be described as an example.
[00146] In the following description, the central geometric axis of the container is defined as a geometric axis that connects the centers of horizontal cross-sectional views of the container in series in the perpendicular direction. The thickness of the reaction container is equivalent to the minimum length of the typical lengths of the reaction container in a horizontal cross-section, and the width of the reaction container is equivalent to the maximum length of the typical lengths of the reaction container in a horizontal plane. In a case where the container is a cylinder, the width and thickness of the container can be replaced by the diameter.
Reaction container material [00147] Any material can be used as a material for reaction container 111 as long as the material has a strength large enough to retain the catalyst, thermal resistance and corrosion resistance against a fluid participating in the catalytic reaction, and resistance to contamination against a reaction product. Examples of the material that can be used include metallic materials such as carbon steel, stainless steel, a nickel alloy, copper, a copper alloy, aluminum, an aluminum alloy, titanium and a titanium alloy; ceramic materials (including processed ceramic materials for bricks) such as silica, alumina, silicon nitride and silicon carbide; and glass materials such as sodium glass and fused silica.
Reaction container dimensions [00148] The lower limit of the reaction container thickness is required to be equal to or greater than the typical dimension (eg diameter) of the fibrous catalyst (eg 10 mm or more). Generally, in the catalytic reaction, heat is generated or absorbed and heat
39/137 communicates with the outside through the surface of the reaction container and, therefore, there is an upper limit for the thickness of the catalytic reaction to guarantee the conduction of heat into the interior of the catalytic reaction container. The upper limit value can be determined from the engineering point of view depending on the reaction heat, the flow rate, the thermal conduction characteristics, and the like (for example, 200 mm).
[00149] There is no particular limitation with the width of the reaction container in terms of function. The width can be determined from the engineering point of view based on the volume of the catalyst layer to be retained and the thickness of the reaction container taking into account strength and structure limitations (eg 5,000 mm).
[00150] The height of the reaction container is required to be equal to or greater than the height of the catalyst layer. However, there is no particular limitation on the upper limit with the height of the reaction container in terms of function, and can be determined from an engineering point of view taking into account the strength and structure limitations (for example, 5,000 mm).
Catalyst layer retainer [00151] As the retainer 112 that supports the catalyst layer 113, it is possible to use a net, punching metal, a retainer obtained by arranging a plurality of rods parallel to each other in a horizontal direction of so as to form spaces between the rods, and fixing both ends of the rods, or the like. The retainer 112 shown in FIGS. 1A, 1B and 1C is an example of a retainer produced by securing both ends of a plurality of rods 118 with the use of securing tools 119.
[00152] When the orifice ratio of retainer 112 is decreased, the ventilation property or transmission property of solid carbon or the like deteriorates. At a high orifice ratio, seen
40/137 that the portion of the retainer that holds the catalyst is decreased, the strength of the retainer becomes insufficient. In any of the types of retainers described above, the orifice ratio of retainer 112 is preferably in the range of approximately 30% to 70%.
[00153] The material for retainer 112 is preferably a metallic material that has thermal resistance, corrosion resistance and strength. Examples of the metallic material described above include stainless steel, a Ni alloy such as HASTELLOY (trademark) or INCONEL (trademark), titanium, a titanium alloy, and the like. Mechanism for activating the catalyst layer [00154] In the embodiment, the catalyst layer 113 in the retainer is moved up and down in the reaction container 111 by moving the retainer 112 up and down. Therefore, the reaction container 111 of the modality is equipped with the drive mechanism 120 which moves the catalyst retainer 112 up and down. Like the drive mechanism 120, it is possible to use a common drive mechanism such as an air cylinder or the up and down movement apparatus 121 in which a gear such as a rack and pinion is used. Retainer 112 is coupled with the up and down movement apparatus 121 using the driving axis 122. When the up and down movement apparatus 121 is operated, the entire retainer 112 is moved along the line axial portion of reaction container 111, thereby moving the entire catalyst layer 113 up and down along the axial line of reaction container 111 as well.
[00155] At least a part of the driving geometry axis 122 on the retainer side 112 is required to be inside the reaction container 111 or the raw material gas inflow path 116 or the reformed gas efflux path 117 which may be present in the bottom section of the reaction container 111. The motion apparatus
41/137 up and down 121 can be supplied outside the reaction container 111. In a case where the reaction container 111 is arranged in a heating device (not shown) such as a heating oven, it is also It is possible to supply the up and down movement device 121 outside the heating device. In such a case, a commercially available up and down motion apparatus may be used, and it is preferable to seal a portion where the driving geometry axis 122 penetrates the reaction container 111 through the packaging or the like for high temperature use.
[00156] In a case where the entire drive mechanism
120 is provided in reaction container 111 as shown in FIGS. 1A, 1B and 1C, the up and down motion apparatus
121 preferably has thermal resistance and corrosion resistance to protect the apparatus from movement up and down, for example, from a high temperature or corrosive substance in reaction container 111. What has been described above can be accomplished, as an example, producing the entire air cylinder of the drive mechanism 120 using a thermally resistant alloy such as HASTELLOY (trademark). In this case, an air supply tube (not shown) to the air cylinder penetrates the reaction container 111; however, since the air supply tube is an immobile section, the air supply tube can be sealed by welding the entire circumference of the tube.
[00157] During the lifting of the retainer, there is a case where a part of the retainer 112 cuts through the catalyst layer 113 (particularly, in a case where a pin type retainer is used as in a second embodiment that will be described subsequently ) and, therefore, it is preferred to activate the retainer 112 not only during the raising of the retainer, but also during the lowering of the re42 / 137 tentor.
Up and down stroke of the retainer [00158] To cause the catalyst particles to move sufficiently with respect to each other, the up and down stroke of the retainer 112 is preferably large. For example, although it can be said that, even at an up and down stroke of approximately 10% of the typical dimension (for example, the diameter) of the external surface of the catalyst, a vibration effect can be obtained and, therefore, a certain degree of an effect that removes the substance accumulated on the catalyst surface as solid carbon can be obtained, the up and down stroke of retainer 112 is preferably 50% or more and more preferably 100% or more of the typical dimension of the external catalyst surface to obtain a sufficient accumulated substance removal effect.
[00159] However, in a case where the up and down stroke is extremely large, an increase in the sizes of the reaction container 111 and the drive mechanism 120 is caused, which is not efficient. In addition, the repetition of the up and down movement with a small stroke (100% or more) also produces the same effect as a larger up and down stroke. Therefore, the up and down stroke is preferably 10% or less of the typical dimension of the external surface of the catalyst.
[00160] (Movement speed up and down) [00161] The required lifting force required to raise the catalyst layer 113 together with the retainer 112 decreases as the lifting speed decreases. As a result of the inventors' investigation, it was observed that the required lifting force required to raise the catalyst layer together with the retainer by 10 mm / s is preferably set to twice or more the required lifting force required to raise the layer in vane
43/137 lyser together with the retainer at 1 mm / s. In addition, at a high lifting speed, the catalyst is susceptible to being broken. Therefore, the lifting speed is preferably small. However, since there is only a small difference in the required lift force between the lift speed of 1 mm / s and the lift speed of 0.5 mm / s, it is not always necessary to set the lift speed to less than 1 mm /s. In addition, the elevation speed of 10 mm / s can be applied as long as the catalyst does not break.
[00162] The average lowering speed of the retainer is preferably higher than the average lifting speed as described above. Particularly, when the retainer is lowered at a speed that is greater than the free fall rate of the catalyst particles at the bottom end (for example, 100 mm / s), part of the catalyst particles is separated from the retainer in order to decrease the bond between the catalyst particles, and the relative movement between the catalyst particles can be increased, which is preferred. However, even when the retainer is lowered at a speed that is extremely greater than the free fall rate of the catalyst particles, the same effect can be achieved.
Catalyst particle size [00163] Generally, the catalyst produced by carrying a substance that has a catalytic action on a porous carrier is required to remain in the catalyst layer 113 located on the retainer 112. Therefore, the catalyst particles are required for have a size that does not have the capacity to penetrate the openings in retainer 112.
Catalyst particle shape [00164] As described above, there is a lower limit value for
44/137 the minimum dimension of the typical dimensions of the same external surface of the catalyst when the catalyst is retained in a specific retainer. In a case where the volume of the catalyst layer 113 is constant, it is common for the total catalyst surface area to increase as the number of catalyst particles increases, and it is possible to improve the reaction rate of the reaction container 111 Therefore, spherical or substantially spherical catalyst particles are preferred since it is easy to increase the number of catalyst particles in a constant volume. It is also preferred that the catalyst particles have a shape that can produce a larger surface area while producing the same volume surrounded by the outer circumferences of the catalyst particles, such as a cylindrical shape or a ring shape. On the other hand, a rod shape or a disk shape is not preferred since it is difficult to retain the catalyst particles.
[00165] During the elevation of the catalyst layer 113, the force acting between the catalyst particles becomes more isotropic in the catalyst layer as the catalyst layer moves upwards, the forces as strong as the acting force in the vertical direction to press the catalyst layer 113 upwards are generated in other directions, and a frictional force is generated between the catalyst particles in proportion to the forces described above. The downward component of the frictional force acts as a resistive force against the catalyst layer which is pressed upwards. When the catalyst layer 113 is pressed upwards from the bottom end, the reaction force between the catalyst particles and the force acting between the catalyst particle and the inner wall of the reaction container are large in the bottom section. of the catalyst layer. Since the force acting in the vertical direction on the elevation catalyst layer is required to be equal to or
45/137 greater than the total of the vertical direction components of the resistive force above the location of the force, the force required to press the catalyst layer upward increases abruptly as the location moves downward in the catalyst layer. The pressure force becomes the maximum at the bottom end of the catalyst layer, and when the pressure force is excessive, the rupture of the catalyst or reaction container is caused.
[00166] From the point of view of what has been described above, the height of the catalyst layer is preferably low. A test was conducted in which a common (cylindrical) catalyst that has a crushing force of 100 N and an angle of rest of 35 ° was directly retained using a second type pin retainer that will be described subsequently , and was moved up and down. The results are illustrated in FIG. 5. The horizontal geometric axis of the drawing indicates the ratio of the height of the catalyst layer to the thickness of the reaction container (the aspect ratio of the catalyst layer), and the vertical geometric axis indicates the peak load to press the catalyst upwards which is normalized based on the peak pressure load upwards when the catalyst layer is pressed upwards under specific conditions. From this drawing, it is observed that when the aspect ratio (the ratio of the height of the catalyst layer to the thickness of the reaction container) of the catalyst layer exceeds two, the upward pressure load increases abruptly. In addition, it has been observed that when the aspect ratio (the ratio of the height of the catalyst layer to the thickness of the reaction container) of the catalyst layer is two or less, the catalyst particles are rarely broken. In addition, as described above, the aspect ratio is preferably two or less to relatively move the catalyst particles across the catalyst layer.
46/137 [00167] On the other hand, in a case where the height of the catalyst layer is extremely low, the relative movement between the catalyst particles by the relative movement between the inner wall of the reaction container and the catalyst particle occurs only in a limited range close to the inner wall surface of the reaction container in the thickness of the reaction container direction, and the relative movement between the catalyst particles does not occur in the central part in the direction of the reaction container thickness, which is not preferred . Particularly, in a case where the height of the catalyst is on average equal to or less than the height of two layers of the catalyst particles (the maximum height of two catalyst particles superimposed in the vertical direction), since the connection between the particles of catalyst in the top layer is small, the catalyst particles are packed tightly closed, and cannot be loosely packed, and therefore relative movement is further hampered. Therefore, the height of the catalyst layer is preferably the height of three or more layers of the catalyst particles (the maximum height of three catalyst particles superimposed in the vertical direction), that is, three times or more the maximum value of the typical lengths of the catalyst. external surface of the catalyst.
Catalyst flow [00168] In some cases, the catalyst particles moved upwards together with the retainer 112 in the reaction container 111 cause the suspension (a phenomenon in which the catalyst particles are not lowered due to the occurrence of self-blocking between the particles of catalyst even when retainer 112 is lowered after the catalyst layer 113 moves upwards using retainer 112) in the reaction container. From the point of view of preventing the suspension of the catalyst particles in reaction container 111, the fluidity of the catalyst as a group of granular bodies in the ca
The catalyst layer 113 is preferably low, and the angle of rest is preferably less than 50 °.
[00169] However, during the lifting of the retainer 112, to retain the anisotropy (the upward force component is dominant) of the force supplied to the catalyst layer 113 of the retainer in the catalyst layer to a higher location than the catalyst layer 113 , the fluidity of the catalyst is preferably not extremely low, and the angle of rest is preferably 10 ° or more. This is seen that, as the region in which the force is high, the anisotropy becomes wider in the catalyst layer, the retainer 112 can be moved upwards with a lower thrust force and therefore the particles catalyst are not easily broken. Catalyst material and action [00170] The material or catalytic action of the catalyst to which the continuous fixed bed catalytic reactor of the modality can be applied are not particularly limited as long as the catalyst is a fluid, particularly a catalyst used in a reaction catalytic in which the gas is used as a raw material. The continuous-bed catalytic reactor of the modality can preferably be used for a catalyst used in a catalytic reaction in which the fluid is gas and the products of the catalytic reaction are gas and a solid or liquid substance, preferably in a catalytic reaction in which the catalytic reaction fluid is the gas containing hydrocarbon and the products of the catalytic reaction are gas and a solid or liquid substance, and particularly in a catalytic reaction in which the catalytic reaction fluid is the gas containing tar and the products of the reaction catalytic include solid hydrocarbon or solid carbon.
[00171] Generally, the continuous fixed bed catalytic reactor of the modality can be used widely for an oxide catalyst used in the catalytic reaction described above, and particularly, it can be
48/137 used preferably for an oxide catalyst used in the catalytic reaction where the catalytic reaction fluid is the tar-containing gas and the products of the catalytic reaction include solid hydrocarbon or solid carbon.
[00172] A specific example of the catalyst that can be used preferably in the continuous continuous bed catalytic reactor of the modality is a catalyst for the reforming of tar-containing gas which is an oxide containing nickel, magnesium, cerium and aluminum, includes at least a complex oxide, and does not include alumina as a single compound (WO2010 / 134326). A preferred example of complex oxide is a complex oxide consisting of crystal phases of NiMgO, MgAl2O4 and CeO2, in which, in addition, in the respective crystal phases, the size of the crystallite of the NiMgO crystal phase in a (200) plane obtained from an X-ray diffraction measurement is in a range from 1 nm to 50 nm, the crystallite size of the MgAl ₂ O ₄ crystal phase in a (311) plane is in a range from 1 nm to 50 nm, and the crystallite size of the CeO ₂ crystal phase in a (111) plane is in a range from 1 nm to 50 nm. The catalyst described above has a feature of an ability to convert even tar-containing gas that includes a large amount of hydrogen sulfide generated during the thermal decomposition of a crude carbonaceous material and mainly includes condensed polycyclic aromatic elements that are susceptible to cause the precipitation of carbon in light hydrocarbon which mainly includes hydrogen, carbon monoxide and methane by highly efficient reforming of the accompanying heavy hydrocarbon such as tar and a feature, when catalyst performance is deteriorated, of precipitated carbon removal or sulfur adsorbed on the catalyst by placing at least any of the water vapor and air in contact with the catalyst at a high temperature, recovering
49/137 thereby catalyst performance and enabling stable operation for a long period of time.
[00173] In addition, another specific example of the catalyst that can be used preferentially in the continuous fixed bed catalytic reactor of the modality is a catalyst for the reforming of tar-containing gas which consists of a complex oxide containing nickel, magnesium, cerium , zirconium and aluminum (Unexamined Japanese Patent Application, First Publication #No. 2011-212574). A preferred example of complex oxide is a complex oxide that includes the crystal phases of NiMgO, MgAl ₂ O ₄ and CexZ _r1-x O ₂ (0 <x <1), where, in addition, in the respective crystal phases, the crystallite size of the NiMgO crystal phase in a (220) plane obtained from an X-ray diffraction measurement is in a range from 1 nm to 50 nm, the crystallite size of the MgAl ₂ crystal phase The ₄ in one (311) plane is in a range from 1 nm to 50 nm, and the crystallite size of the CexZ crystal phase _r1-x O ₂ in a (111) plane is in a range from 1 nm to 50 nm nm. According to the catalyst described above, it is possible to steadily convert the tar containing gas generated in the thermal decomposition of coal or biomass into a light chemical substance such as carbon monoxide or hydrogen. Particularly, it is possible to convert evenly the tar containing gas containing a high concentration of hydrogen sulphide into a light chemical substance such as carbon monoxide or hydrogen by placing the tar containing gas in contact with the catalyst without perform a desulfurization treatment in order to reform the tar in the crude gas or reform a hydrocarbon component in the purified gas.
[00174] In addition, another specific example of the catalyst that can be used preferably in the continuous fixed bed catalytic reactor of the modality is a catalyst for the reforming of gas that
50/137 contains tar which is a complex oxide represented by aM * bNi * cMg * dO where a, b and c satisfy a + b + c = 1, 0.02 <a <0.98, 0.01 <b <0 , 97 and 0.01 <c <0.97, d represents a value where oxygen and a positive element become electrically neutral, and M represents at least one element selected from Li, Na and K (Patent Application Unexamined Japanese, First Publication #No. 2011-212552, Unexamined Japanese Patent, First Publication #No. 2011-212552 and Unexamined Japanese Patent Application, First Publication #No. 2011-212598). A preferred example of a complex oxide is a complex oxide formed by adding at least one oxide selected from silica, alumina and zeolite, in which, in addition, the amount of at least one oxide selected from silica, alumina and zeolite it is preferably in a range of 1 mass% to 90 mass% in relation to all complex oxide. According to the catalyst described above, it is possible to steadily convert the tar containing gas generated in the thermal decomposition of coal or biomass into a light chemical substance such as carbon monoxide or hydrogen. Particularly, it is possible to convert evenly the tar containing gas containing a high concentration of hydrogen sulphide into a light chemical substance such as carbon monoxide or hydrogen by placing the tar containing gas in contact with the catalyst without perform a desulfurization treatment in order to reform the tar in the crude gas or reform a hydrocarbon component in the purified gas.
[00175] (Other applicable examples) [00176] The invention can preferably be used in the continuous continuous bed catalytic reactor where coking or the like occurs in addition to the continuous fixed bed catalytic reactor and catalyst exemplified above.
51/137 [00177] 1) Methane reforming catalytic reactor: Examples
Comparatives in Unexamined Japanese Patent Application, First Publication #No. 2006-35172 describe that a large amount of coking (carbon precipitation) occurs with the use of methane gas which is hydrocarbon as a raw material gas.
[00178] 2) Commercially available catalytic gas reforming reactor: Patent Document 2 describes examples of coking.
[00179] 3) Additionally, the invention can be applied to a catalytic reactor to reform a variety of purified petroleum gases such as LPG or natural gas, a catalytic reactor for a fuel cell in which the gas containing hydrogen and an oxidizer gases are created to act, thereby generating power and water as a by-product (for example, Unexamined Japanese Patent Application, First Publication #No. 2009-48797), and the like. [00180] (Second embodiment) [00181] Next, a continuous fixed bed catalytic reactor according to a second embodiment will be described with reference to FIGS. 2A, 2B and 2C. FIG. 2A is a plan view, FIG. 2B is a front view, and FIG. 2C is a side view. A continuous fixed bed catalytic reactor 110 of FIGS 2A, 2B and 2C is the same as the continuous fixed bed catalytic reactor of the first embodiment described with reference to FIGS 1A, 1B and 1C except that several pins are used in a catalyst retainer as illustrated in FIG. 7.
[00182] In the present embodiment, the reaction container 111 includes a catalyst retainer 112 'in a bottom section which is an inflow opening for the reaction container 111. The catalyst retainer 112' is a structure that has several pins 125 retained on a bottom plate 126, and is a catalyst retention unit that directly retains a fibrous catalyst in the catalyst layer
52/137
113 in the front end sections of pins 125. When pins 125 are provided at intervals that are smaller than the size of the fibrous catalyst, it is possible to retain the fibrous catalyst in the front end sections of pins 119, and the intervals between the pins they function as inflow openings for the catalytic reaction fluid or efflux openings for a generated fluid.
[00183] In the illustrated catalyst retainer 112 ', pins 125 can be produced using, for example, round rods. Pins 125 are generally of the same shape, but need not necessarily be of the same shape. The pins can have different shapes as long as the fibrous catalyst is retained directly in the front end sections of pins 125, and a fluid can communicate through the gaps between pins 125. The pins can have different sizes, lengths and angles, and the pin shape is not limited to a linear shape. In the illustrated catalyst retainer 112 ', the front ends of pins 125 are formed in the same plane, but the front ends of pins 125 can be formed on a curved surface, and exceptionally, part of the pins can protrude from the surface forming the front ends . According to the catalyst retainer described above 125, a high orifice ratio and blocking impedance are realized. In addition, in the embodiment, the fibrous catalyst is retained directly by the front end sections of the pins 125, but the fibrous catalyst can be retained substantially and directly by the front end sections of the pins, for example, retaining the catalyst with the pins covered with a cover that has a shape similar to the pin.
[00184] In relation to the arrangement of pins 125 in the catalyst retainer 112 ', when the center of the pin in a plane perpendicular to the geometric axis of the pin is considered as a point, all tri
53/137 angles formed by the centers of three adjacent pins are preferably identical isosceles triangles, and particularly equilateral triangles. Then, it is possible to create a catalyst retention structure with a minimum number of pins in relation to the required cross-sectional area of the catalyst retained by the pins.
[00185] All pins 125 are preferably arranged so that the central geometric axes of the pins are in parallel with each other. This is seen as the openings on the side surfaces of the pins become uniform, and become more difficult to block. In a portion where the pin shafts are extremely close to each other, blocking is likely to occur between the lateral surfaces of the pins. The lengths of portions on the pins in parallel with each other are determined so that the spaces that allow free communication of a raw material fluid or a reformed fluid without blocking the voids between the pins are formed.
[00186] In a case where design convenience or similar is required, the geometric axis lines of pins 25 may not be parallel to each other by defining the distance between the central geometric axes to gradually increase or decrease towards the catalyst. Similarly, the intervals between the pins can be set to increase or decrease gradually while the central geometric axes of the pins are in parallel with each other. The lengths of portions on the pins substantially in parallel with each other are determined so that spaces that allow free communication of a reaction fluid without blocking the voids between the pins are formed.
[00187] In relation to the intervals between the pins, the distance between the geometric axes excluding the diameter (outer diameter dimension) of all pins is required to be less than the dimension
54/137 minimum mesh size (sieve opening dimension) that allows catalyst communication particularly at the tip (the front end sections of the pins) of the catalyst retainer. Then, the fibrous catalyst can be supported by the pins without the fibrous catalyst being dripped into the spaces between the pins. Although it may be the case that the dimensions of some catalyst become exceptionally smaller than the distance between the geometric axes excluding the diameters of the pins so that the catalyst is dripped into the spaces between the pins as small pieces of the catalyst generated due to disruption of the catalyst, when sufficient storage space for a dripped substance is provided in the bottom section of the catalyst retainer 112 'and below the catalyst retainer, that is, a space to store displaced liquid or solid substances (including a reaction product , top stream dust and the like) generated in the catalyst layer is provided in the catalyst layer, there is no particular problem at least from the point of view of blockage in the catalytic reaction container. In addition, in a case where the storage space described above is provided, displaced substances can be removed more easily from the device. From the point of view of the ventilation property and the blocking resistance of the retainer, the orifice ratio (1- [the total cross-sectional area of the pins] / [the apparent cross-sectional area of the flow paths]) in a cut perpendicular to the direction of the main ventilation current is preferably 90% or more. The upper limit of the orifice ratio is limited by the cross-sectional area of individual pins determined based on the warping strength of the pins or the like.
[00188] The lengths of the pins are preferably established to satisfy [00189] [the cross-sectional area of apparent flow of an open
55/137 gas inflow structure (outflow opening) for a fluid]> [the cross sectional area of apparent flow for a fluid in the catalytic layer].
[00190] When the thickness and width (diameter) of the catalytic reaction container are given, the apparent flow cross-sectional area of the inflow opening (efflux opening) for a fluid can be adjusted by changing the height of the pins . However, in a case where the apparent flow cross-sectional area for a fluid is extremely large in the catalytic layer (the reaction container is flat in the direction of the main stream, or similar), the method described above is not always true. Here, the cross-sectional area of apparent flow for a fluid refers to the area of a region surrounded by the side walls of the catalytic reaction container in a plane perpendicular to the main stream of the raw material fluid or the reformed fluid.
[00191] The value of the aspect ratio (length to diameter ratio) of the pin is preferably 100 or less, and more preferably 20 or less from the point of view of warping prevention. However, in a case where the maximum load applied to the pin is small enough, the aspect ratio may be greater than the values described above. In addition, to establish an apparent flow cross-sectional area for a sufficiently large fluid in the inflow opening (outflow opening), the pin aspect ratio is preferably 1 or more, and more preferably 5 or more.
[00192] Any material can be used as a material for the pin as long as the material has a strength large enough to maintain the thermal resistance and corrosion resistance of the catalyst against a fluid with which the material is brought into contact, and contamination resistance against a reaction product. Examples of the ma
56/137 material that can be used include metallic materials such as carbon steel, stainless steel, a nickel alloy, copper, a copper alloy, aluminum, an aluminum alloy, titanium and a titanium alloy; ceramic materials such as silica, alumina, silicon nitride and silicon carbide; and glass materials such as sodium glass and fused silica. Since the catalytic reaction container for reforming tar is generally operated at a high temperature of 800 ° C or higher, stainless steel or nickel alloy such as HASTELLOY (registered trademark) or INCONEL (registered trademark) are particularly preferred shares.
[00193] The method for fixing the pins to the bottom plate has no particular limitation and, for example, all pins can be fixed to the bottom plate by welding.
[00194] Since the use of the catalyst retainer described above enables the maintenance of force even when a large orifice ratio is established, unlike the case in which a puncture metal or mesh is used, it is possible to establish a ratio of substantial orifice (the ratio of spaces, in a perpendicular plane, to the geometric axes of the pin in the contact portions of the pin arrangements with the catalyst) at a high value of 90% or more, which is a value that could not be realized in related technique. A value of 95% or more is also possible.
[00195] Furthermore, since the respective pins 125 in the catalyst retainer 112 'are all isolated in cross-section perpendicular to the central geometric axes of the pins, and that the spaces extending between the pin arrangements are coupled together, even when a solid substance such as carbon is precipitated on the surfaces of the pins, the solid substance is trapped between adjacent pins, which in this way avoids the easy occurrence of blockage in the opening. [00196] The fibrous catalyst in the catalytic layer 113 in the container
57/137 of reaction 110 of the modality is required to satisfy the dimensional limitations of the pins. For example, a catalyst from the following example 1 can be used.
(Example 1) [00197] In a case where spherical particles of fibrous catalyst that have a diameter of 10 mm are loaded into a cylindrical container of the catalytic reaction that has an apparent cross-sectional diameter of 100 mm, the height of the pin it simply needs to be 100 mm. Meanwhile, since the pin diameter can be set at 5 mm, at this point, the pin's aspect ratio is approximately 20, which is achievable.
[00198] On the other hand, a catalyst of the following example 2 is not preferable since the dimensional limitations of the pins cannot be satisfied.
(Example 2) [00199] In a case in which spherical particles of fibrous catalyst that have a diameter of 0.1 mm are loaded into a cylindrical container of the catalytic reaction that has an apparent cross-section of 100 mm, the pin heights they are required to be at least several tens of millimeters. Meanwhile, the diameter of the pin is required to be smaller than the diameter of the fibrous catalyst particle. Therefore, the aspect ratio of the pin exceeds 100, which is not preferable.
[00200] The dimensions of the catalyst are determined depending on the efficiency of the catalytic reaction and are, therefore, fickle. The intervals between the pins on the catalyst retainer can be determined by considering the dimensions of the catalyst; however, depending on the need, it is also possible to determine the dimensions of the catalyst by considering the intervals between the pins in the catalyst retainer.
58/137 [00201] As described above, when the catalyst is retained in a specific catalyst retainer, there is a lower limit value for the minimum dimension of the typical dimensions of the same external surface of the catalyst. In a case where the volume of the catalytic reaction container is constant, it is common for the total catalyst surface area to increase as the amount of catalyst particles increases, and it is possible to improve the reaction rate of the reaction container. Therefore, spherical or substantially spherical catalyst particles are preferred since it is easy to increase the amount of catalyst particles in a constant volume. In addition, it is also preferred that the catalyst particles have a shape that can produce a larger surface area while producing the same volume surrounded by the outer circumferences of the catalyst particles, such as a cylindrical shape or a ring shape.
[00202] On the other hand, a format such as a disk format in which only a typical length in a single direction is extremely small is generally not preferred, since it is difficult to maintain the catalyst particles (comparison: in a network or puncture metal of the related technique, a disk that was marginally larger than the mesh size dimension was a shape that could further increase the amount of catalyst particles). In addition, a rod shape is also not preferred since it is difficult to maintain the catalyst particles, as the related technique.
[00203] The external dimensions of the fibrous catalyst are preferably in a range of approximately 5 mm to 50 mm from the point of view of the ease of retaining the catalyst in the catalyst retainer and ensuring a high specific surface area for reactivity.
[00204] In the modality also, the material or action of the catalyst are the same as in the first modality previously described59 / 137 ta.
[00205] The catalyst retainer 112 'of the embodiment can be moved up and down using the drive mechanism 120, as well as the retainer 112 in the first embodiment previously described with reference to FIGS. 1A, 1B and 1C and, consequently, the catalytic layer 113 in reaction container 111, can be moved up and down. As the drive mechanism 120, it is possible to use a common drive mechanism, such as an air cylinder or the up and down movement apparatus 121, in which a gear such as a rack and pinion is used, which has been previously described in the first embodiment, and the retainer 112 'is coupled to the up and down movement apparatus 121 using the driving axis 122.
Third modality [00206] Next, a continuous fixed bed reactor according to a third modality will be described with reference to FIGS. 3A, 3B and 3C. FIG. 3A is a plan view, FIG. 3B is a front view, and FIG. 3C is a side view. A continuous fixed bed reactor 110 of FIGS. 3A, 3B and 3C is the same as the continuous fixed bed reactor of the second embodiment described with reference to FIGS. 2A, 2B and 2C except for the drive mechanism to move the catalyst retainer up and down.
[00207] While in the second embodiment the drive mechanism 120 for moving the catalyst retainer 112 'up and down moves the retainer 112' along the geometric axis line of the reaction container 111, in the third embodiment, the retainer 112 ' employs a cantilevered configuration in which one end of the bottom plate 126 is connected to a axis of rotation 127 and the other end is connected to the driving axis 122 of the drive mechanism 120. When the catalyst particles are made
60/137 move relative to each other by moving a single side (the left side in FIG. 3B) of retainer 112 'up and down using the drive mechanism 120, it is possible to efficiently remove a generated solid product and accumulated in the catalytic layer 113. In the modality, due to an effect that shears-deforms the entire catalytic layer, it is possible to supply a large relative displacement between the catalyst particles with the same beat up and down compared to the movement method for up and down the second mode, and the like. In addition, when lifting the retainer, all the front end sections of the pins in the retainer move in the direction of the axis of rotation 127. Therefore, to prevent the fall of the catalyst particles from the pins, caused by the interference between the pins and the adjacent inner wall of the reaction container, or an increase in the span using the movement of the front ends of the pins, the pins on the retainer can be previously arranged inclined towards the drive mechanism 120. Fourth to sixth modalities [00208] , embodiments four to six of the invention will be described in detail with reference to the accompanying drawings. Meanwhile, in the description and drawings below, components that have substantially the same function will be provided with the same numerical references, and their duplicate description will not be made.
Fourth modality
General structure [00209] As an example of a continuous fixed bed reactor, a plan view, a front view, and a side view are illustrated in FIGS 8A, 8B and 8C, and an enlarged cross-sectional view obtained along line XX in FIG. 8B is illustrated in FIG. 8D.
[00210] The catalyst reaction container 211 has a cross-section
61/137 rectangular salt in a horizontal plane, although not limited to it, accommodates catalytic layer 212 in which the fibrous catalyst particles are randomly laminated, is connected to an inflow tube 213 for a reaction fluid 216 through an opening inflow 213a in the lower section, and is connected to an efflux tube 214 for reformed fluid 217 through an outflow opening 214a in the upper section. The numerical reference 215 represents a top of the catalyst reaction container to feed the catalyst into the reaction container and remove the catalyst from the offline catalyst container. The catalytic reaction container 211 has a catalyst retainer 218 in the inflow opening portion 213a at the bottom as shown in cross-section X-X. Although not illustrated in the drawings, it is also possible to arrange the continuous fixed bed reactor in a heating furnace and supply a temperature and heat necessary for the catalytic reaction.
[00211] The catalyst retainer 218 is a structure that has a number of pins 219 retained on a bottom plate 220 in the bottom sections of the pins as illustrated in FIG. 9, and it is a catalyst retainer unit that retains a fibrous catalyst 212 in the front end sections of pins 219. When pins 219 are provided at intervals that are smaller than the size of fibrous catalyst 212, it is possible to maintain the fibrous catalyst 212 in the front end sections of the pins 219, and the gaps between the pins act as inflow openings for the raw material fluid or efflux openings for a reformed fluid.
[00212] In catalyst retainer 218, pins 219 have the same shape, but not necessarily the same shape. As long as the fibrous catalyst can be retained in the front end sections of the pins, and a fluid can be communicated through the gaps between the pins, the pins can have sizes, lengths and angles
62/137 different, and the shape of the pin is not limited to a linear shape. [00213] On catalyst retainer 218, the front ends of pins 219 are formed in the same plane, but the front ends of pins 219 can be formed on a curved surface, and exceptionally, some of the pins may protrude from the surface forming the ends front.
[00214] According to the catalyst retainer 218 described above, a high orifice ratio and the prevention of blockage are realized.
Pin arrangement on the catalyst retainer [00215] FIG. 10 illustrates a view of the arrangement of pins 219 in the catalyst retainer illustrated in FIG. 9 is seen from the side of the front ends of the pins (a plane perpendicular to the geometric axis of the pin) and an enlarged view of part of the arrangement. When the center of the pin in a plane perpendicular to the geometric axis of the pin is considered as a point, the triangles formed by the centers (α, β and γ in FIG. 9) of three adjacent pins are preferably identical isosceles triangles, and particularly equilateral triangles . Then, it is possible to create a catalyst retaining structure with a minimum number of pins in relation to the required cross-sectional area of the catalyst retained by the pins.
[00216] All pins are preferably arranged in such a way that the central geometric axes of the pins are in parallel with each other. This is due to the fact that the openings on the side surfaces of the pins become uniform, and more difficult to block. In portions where the geometric axes of the pins are extremely close to each other, spaces between the lateral surfaces of the pins are highly likely to be blocked. The lengths of portions on the pins in parallel with each other are determined so that spaces allow the free communication of a fluid
63/137 of raw material or one of reformed fluid without blocking spans between the pins being formed.
[00217] In a case in which design convenience or similar are required, the geometric axis lines of pins 25 may not be parallel to each other by establishing that the distance between the central geometric axes gradually increases or decreases in the direction of the catalyst . Similarly, the intervals between the pins can be set to gradually increase or decrease while the central geometric axes of the pins are in parallel with each other.
[00218] The lengths of portions on the pins in substantial parallel with each other are determined so that spaces are formed that allow the free communication of a reaction fluid without blocking the gaps between the pins.
Pin intervals [00219] It is preferable to arrange the pins as shown in FIG. 9, in which case, the intervals between the pins desirably satisfy the following formula:
[00220] [the distance between the geometric axes of the pins] - [the dimension of the outside diameter of the pin] <[the minimum dimension of mesh size that allows communication of the catalyst] [00221] [the dimension of the outside diameter of the pin] : the dimension of the outer diameter of the pin refers to the total radii (the distance from the geometric axis of the pin to the outer diameter) between the geometric axes of two pins, and refers to the diameter of the pin in the arrangement of preferred cylindrical pins.
[00222] mesh: an opening in tamis [00223] mesh size dimension: although the mesh size dimension is based on a common definition such as JIS, which has a presumption that the opening has a square format
64/137 dated, in the modality, the mesh size dimension is equivalent to the minimum dimension of the typical dimensions (diameter, height and the like) of the external shape of a single fibrous catalyst particle. [00224] That is, the distance between the geometric axes excluding the diameter (outer diameter dimension) of all pins, is less than the minimum mesh size dimension that allows the catalyst communication particularly at the tip (the front end sections of the pins) of the catalyst retainer, the fibrous catalyst can be supported by the pins without the fibrous catalyst being dropped in spaces between the pins. Although there may be a case in which the dimensions of some catalyst exceptionally become smaller than the distance between the geometric axes with the exclusion of the diameters of the pins, so that the catalyst is dropped in the spaces between the pins as small parts of the generated catalyst due to the breakdown of the catalyst, when sufficient storage space for the fallen substance is provided in the lower section of the catalyst retainer 218 and below the catalyst retainer, that is, a space for storing lost solid or liquid substances (which includes a reaction product, dust from the upper stream, and the like) is provided in the catalytic layer, there is no particular problem, at least from the point of view of blocking in the catalytic reaction container. In addition, in a case where the storage space described above is provided, lost substances can be more easily removed from the device. From the point of view of the ventilation property and resistance to blocking of the retainer, the orifice ratio (1- [the total cross-sectional area of the pins] / [the apparatus cross-sectional area of the flow paths]) in a cut perpendicular to the main current ventilation direction is preferably 90% or more. The upper limit of the orifice ratio is limited by the cross-sectional area of
65/137 individual pins determined based on the resistance to warping of the pins.
[00225] Since the use of the catalyst retainer described above enables the maintenance of force even when a large orifice ratio is established, unlike the case in which a puncture metal or mesh is used, it is possible to establish a ratio of substantial orifice (the ratio of spaces, in a perpendicular plane, to the geometric axes of the pin in the contact portions of the pin arrangements with the catalyst) at a high value of 90% or more, which is a value that could not be realized in related technique. A value of 95% or more is also possible.
[00226] Furthermore, since the respective pins 219 in the catalyst retainer 218 are all isolated in cross-section perpendicular to the central geometric axes of the pins, and that the spaces extending between the pin arrangements are coupled together, even when a solid substance such as carbon is precipitated on the surfaces of the pins, the solid substance is trapped between adjacent pins, which thus avoids the easy occurrence of blockage in the opening. Pin shape [00227] The pin preferably has a round rod shape (a column shape) since the round rod shape has a smooth surface and does not easily damage the catalyst. The shape of the pin can be a square column shape or other shapes for convenience of manufacture. From the point of view of warping prevention, the central geometric axis is preferably linear. The pin may have a curved bar shape for the sake of manufacturing convenience or design convenience.
Pin shape in the contact portion of the pin with the catalyst [00228] The shape of the pin in the contact portion of the pin with the catalyst, that is, substantially, the shape of the front end of the
66/137 pin, is desirably a shape that suppresses the rupture of the catalyst during contact with the catalyst.
[00229] The front end of the pin can be flat. In a case in which the fibrous catalyst particles have a spherical shape, the contact area becomes the largest (ie, the surface pressure becomes the smallest) when the retaining surface in a catalyst retention mechanism is a plate flat, and the catalyst particles are less likely to be broken (in fact, the contact area becomes larger when the fibrous catalyst particles come into contact with a concave surface; however, when an amount of fibrous catalyst particles comes into contact with the retaining surface at the same time, it is not possible to create a shape that provides a concave surface everywhere). In a case in which the flat section of the front end of the pin which is the retaining surface comes into contact with the fibrous catalyst particle, when the width of the flat section is sufficiently wide (for example, 0.1 mm ² or more), the contact surface pressure at that time is equal to the contact surface pressure in a case where the catalyst particles come into contact with a flat plate, and it is possible to make the catalyst particles less likely to break. In a case where the front end of the pin is made to be flat, when the connecting sections of the flat section of the pin and the side surface of the pin are facing each other, it is possible to reduce the surface pressure in one case where the catalyst particles come into contact with the connecting sections.
[00230] In addition, it is possible to supply the front end of the pin with a semi-spherical shape that has the same diameter as the pin. In the case of columnar particles of fibrous catalyst, since there is an extremely large curvature (angle (corner)) in the section of
67/137 connection between the bottom surface and the lateral surface of the column, in the catalyst particles that have the shape described above, there is a concern that a defect in a corner section may act as the major cause of damage to the catalyst and therefore, it is possible to avoid damage to the catalyst by supplying the catalyst particles with a semi-spherical shape. Furthermore, when [00231] [the maximum curvature of the fibrous catalyst]> [the curvature of the front end of the pin] [00232] is satisfied, more specifically, when the curvature of the contact portion of the pin with the particle of fibrous catalyst is less than the maximum curvature of the extreme outer surface of the fibrous catalyst particle, the contact surface pressure of the catalyst becomes insignificantly different from the contact surface pressure when the catalyst particles come into contact with a plane, and it is possible to make the particles are less likely to break.
Pin dimensions [00233] The pin size is preferably less than [the minimum mesh size dimension that allows the catalyst to communicate], and more preferably 1/3 or less than [the minimum mesh size dimension that allows the communication of the catalyst] from the point of view of guaranteeing the orifice ratio. In a case in which the catalyst particles have a shape that includes a hole such as a ring shape or a cylindrical shape, the pin size is established to be larger than the diameter of the catalyst hole. [00234] The length of the pin is preferably established to satisfy [00235] [the cross sectional area of apparent flow of a gas inflow opening (outflow opening) for a fluid]> [the cross sectional area of apparent flow for a fluid in the catalytic layer 68/137 ca].
[00236] When the thickness and width (diameter) of the catalytic reaction container are given, the apparent flow cross-sectional area of the inflow opening (efflux opening) for a fluid can be adjusted by changing the height of the pins. However, in a case where the apparent flow cross-sectional area for a fluid is extremely large in the catalytic layer (the reaction container is flat in the direction of the main stream, or similar), the method described above is not always true. Here, the cross-sectional area of apparent flow for a fluid refers to the area of a region surrounded by the side walls of the catalytic reaction container in a plane perpendicular to the main stream of the raw material fluid or the reformed fluid.
[00237] The value of the aspect ratio (length to diameter ratio) of the pin is preferably 100 or less, and more preferably 20 or less from the point of view of warping prevention. However, in a case where the maximum load applied to the pin is sufficiently small, the value of the aspect ratio may be greater than the values described above. In addition, to establish an apparent flow cross-sectional area for a sufficiently large fluid in the inflow opening (outflow opening), the pin aspect ratio is preferably 1 or more, and more preferably 5 or more.
Pin material [00238] Any material can be used as a pin material as long as the material is strong enough to maintain the thermal resistance and corrosion resistance of the catalyst against a fluid with which the material is placed contact, and resistance to contamination against a reaction product. Examples of the material that can be used include metallic materials such as steel
69/137 carbon, stainless steel, a nickel alloy, copper, a copper alloy, aluminum, an aluminum alloy, titanium and a titanium alloy; ceramic materials such as silica, alumina, silicon nitride and silicon carbide; and glass materials such as sodium glass and fused silica. Since the catalytic reaction container for reforming tar is generally operated at a high temperature of 800 ° C or higher, stainless steel or nickel alloy such as HASTELLOY (registered trademark) or INCONEL (registered trademark) are particularly preferred shares.
Method for fixing the pins [00239] The method for fixing the pins to the bottom plate is not particularly limited and, for example, a catalyst retainer substrate, where all the pins can be fixed by welding, is provided.
Pin arrangement [00240] In the catalyst retainer of the embodiment, the pins are preferably arranged in parallel to each other as shown in FIG. 9, but are not necessarily parallel to each other, and even when the gaps between the pins are different, a desired effect can be obtained. For example, as described above, the pins can be uniformly or separately curved (in the latter case, the pins are not in parallel with each other) rather than being linear. Additionally, the pins can be erected from the bottom plate at different angles of inclination or in different directions of inclination, and even in this case, a desired effect can be obtained.
[00241] For example, according to an exemplary modification illustrated in FIG. 11, pins 219 can erect radially in catalyst retainer 218. Meanwhile, in FIG. 11, the reference numeral 211 represents the continuous fixed bed reactor, the
70/137 reference 212 represents the catalytic layer, and the pin retaining member does not have a plate shape, and is installed in a location other than that in FIGS. 8A, 8B, 8C and 8D.
Catalytic reaction container format [00242] Any format can be applied as long as the catalytic reaction container has openings at both ends and is capable of storing the catalyst (that is, a tubular shape) between the openings. For example, the catalytic reaction container may have a cylindrical shape, rectangular duct shape or the like. Next, the description will be conducted on the assumption that the container has a rectangular duct shape.
[00243] The central geometric axis of the container is defined as a geometric axis that connects the centers of horizontal cross-sectional views of the container in series in the perpendicular direction. In a case where the container is a cylinder, in the description below, the width and thickness of the container can be replaced by the diameter.
Material for the catalytic reaction container [00244] Any material can be used, as long as the material has a strength large enough to maintain the thermal resistance and corrosion resistance of the catalyst against a fluid that participates in the catalytic reaction, and the resistance to contamination against a reaction product. Examples of the material that can be used include metallic materials such as carbon steel, stainless steel, a nickel alloy, copper, a copper alloy, aluminum, an aluminum alloy, titanium and a titanium alloy; ceramic materials (which include ceramic materials processed into bricks) such as silica, alumina, silicon nitride and silicon carbide; and glass materials such as sodium glass and fused silica.
Dimensions of the catalytic reaction container
71/137 [00245] In a case where heat is generated or absorbed due to the catalytic reaction, or in a case where a heat source, a cooler and a heat exchanger are separately supplied in the catalytic reaction container, there is no there are particular upper limits for dimensions in the direction perpendicular to the main stream of a fluid.
[00246] In a case in which heat is generated or absorbed due to the catalytic reaction, and there is no heat exchanger in the catalytic reaction container, it is necessary to communicate heat on the surface of the catalytic reaction container and transfer heat up and into the catalytic reaction container. Therefore, there are upper limits for dimensions in the direction perpendicular to the main stream of a fluid. The upper limit value can be determined from an engineering point of view depending on the reaction heat, flow rate, thermal conduction characteristics, and the like.
[00247] Needless to say, the dimensions of the catalytic reaction container in the direction perpendicular to the main stream of a fluid are required to be larger than the diameter of the fibrous catalyst particles. There is no particular limitation with the dimensions towards the main stream of the catalytic reaction container, as long as the dimensions are equal to or greater than the required length of the catalytic layer towards the main stream.
Dimensions of the fibrous catalyst [00248] The fibrous catalyst used in the modality is required to satisfy the dimensional limitations of the pins. For example, a catalyst from the following example 1 can be used.
(Example 1) [00249] In a case where spherical particles of fibrous catalyst that have a diameter of 10 mm are loaded into a cylindrical container of the catalytic reaction that has a cross section
72/137 apparent of 100 mm, the height of the pin simply needs to be 100 mm. Meanwhile, since the pin diameter can be set at 5 mm, at this point, the pin's aspect ratio is approximately 20, which is achievable.
[00250] On the other hand, a catalyst of the following example 2 is not preferable since the dimensional limitations of the pins cannot be satisfied.
(Example 2) [00251] In a case in which spherical particles of fibrous catalyst that have a diameter of 0.1 mm are loaded into a cylindrical container of the catalytic reaction that has a diameter of 100 mm, the pin heights are required be at least several tens of millimeters. Meanwhile, the diameter of the pin is required to be smaller than the diameter of the fibrous catalyst particle. Therefore, the aspect ratio of the pin exceeds 100, which is not preferable.
[00252] The dimensions of the catalyst are determined depending on the efficiency of the catalytic reaction and are, therefore, fickle. The intervals between the pins on the catalyst retainer can be determined by considering the dimensions of the catalyst; however, depending on the need, it is also possible to determine the dimensions of the catalyst by considering the intervals between the pins in the catalyst retainer.
Fibrous catalyst particle shape [00253] As described above, when the catalyst is retained in a specific catalyst retainer, there is a lower limit value for the minimum dimension of the typical dimensions of the same external surface of the catalyst. In a case where the volume of the catalytic reaction container is constant, it is common for the total catalyst surface area to increase as the amount of catalyst particles increases, and it is possible to improve the reaction rate of the catalyst container.
73/137 reaction. Therefore, spherical or substantially spherical catalyst particles are preferred since it is easy to increase the amount of catalyst particles in a constant volume. In addition, it is also preferred that the fibrous catalyst particles have a shape that can produce a larger surface area while producing the same volume surrounded by the outer circumferences of the catalyst particles, such as a cylindrical shape or a ring shape.
[00254] On the other hand, a shape such as a disk shape in which only a typical length in a single direction is extremely small is not preferred, since it is difficult to maintain the catalyst particles (comparison: in a mesh or metal of puncture of the related technique, a disk that was marginally larger than the mesh size dimension was a shape that could further increase the amount of catalyst particles). In addition, a rod shape is also not preferred since it is difficult to maintain the catalyst particles, as the related technique.
[00255] The external dimensions of the fibrous catalyst are preferably in a range of approximately 5 mm to 50 mm from the point of view of the ease of retaining the catalyst in the catalyst retainer and ensuring a high specific surface area for reactivity. Catalyst material and action [00256] The catalytic material or action of the catalyst to which the continuous fixed bed reactor of the modality can be applied are not particularly limited, as long as the catalyst is a fluid, particularly a catalyst used in a reaction catalytic in which gas is used as a raw material. The continuous fixed bed reactor of the modality can preferably be used for a catalyst used in a catalytic reaction in which the fluid is gas and the products of the catalytic reaction are a gas and a solid or liquid substance, preferably
74/137 primarily in a catalytic reaction in which the catalytic reaction fluid is a gas containing hydrocarbon, and the products of the catalytic reaction are a gas (and a liquid or solid substance), and particularly in a catalytic reaction in which the fluid Catalytic reaction gas is a tar containing gas and the products of the catalytic reaction include solid hydrocarbon or solid carbon.
[00257] Generally, the continuous fixed bed reactor of the modality can be used wisely for an oxide catalyst used in the catalytic reaction described above, and particularly, it can be preferably used for an oxide catalyst used in the catalytic reaction in which the catalytic reaction fluid it is a tar-containing gas, and the products of the catalytic reaction include solid hydrocarbon or solid carbon.
[00258] Generally, the continuous fixed bed reactor of the modality can be used wisely for an oxide catalyst used in the catalytic reaction described above, and particularly, it can be preferably used for an oxide catalyst used in the catalytic reaction in which the catalytic reaction fluid it is a tar-containing gas, and the products of the catalytic reaction include solid hydrocarbon or solid carbon.
[00259] A specific example of the catalyst that can preferably be used in the continuous continuous bed reactor of the modality is a catalyst to reform a gas containing tar, which is an oxide containing nickel, magnesium, cerium and aluminum, which includes at least a complex oxide, which does not include alumina as its own compound (WO2010 / 134326). A preferred example of the complex oxide is a complex oxide made of crystalline phases of NiMgO, MgAl2O4 and CeO2 in which, in addition, in the respective crystalline phases, the crystallite size of the crystalline phase of NiMgO in a plane (200) obtained from a X-ray diffraction measurement is in a range
75/137 from 1 nm to 50 nm, the crystallite size of the crystalline phase of MgAl ₂ O4 in a plane (311) is in a range of 1 nm to 50 nm, and the crystallite size of the crystalline phase of CeO ₂ in a plane (111) is in a range from 1 nm to 50 nm. The catalyst described above has a feature of an ability to convert even tar-containing gas, which includes a large amount of hydrogen sulfide generated during the thermal decomposition of a crude carbonaceous material and mainly includes condensed polycyclic aromatic elements that are likely to cause precipitation of carbon into light hydrocarbon, mainly which includes mainly hydrogen, carbon monoxide and methane by highly reforming the attached heavy hydrocarbon, such as tar, and a feature of, when catalyst performance is deteriorated, removing precipitated carbon or sulfur adsorbed on the catalyst by placing at least any of the water or air vapor in contact with the catalyst at a high temperature, which in this way recovers the catalyst performance and enables stable operation for a long period of time.
[00260] In addition, another specific example of the catalyst that can preferably be used in the continuous fixed bed reactor of the modality is a catalyst to reform tar-containing gases, which is made of a complex oxide containing nickel, magnesium, cerium, zirconium and aluminum (Unexamined Japanese Patent Application, First Publication No. ² 2011-212574). A preferred example of a complex oxide is a complex oxide that includes crystalline phases of NiMgO, MgAl ₂ O ₄ and Ce _x Zr _1-x O ₂ (0 <x <1) where, in addition, in the respective crystalline phases, the size of the crystallite of the NiMgO crystalline phase in a plane (220) obtained from an X-ray diffraction measurement is in a range from 1 nm to 50 nm, the crystallite size of the crystalline phase of MgAl ₂ O ₄ in a plane (311) is in a range from 1 nm to 50 nm, and
76/137 the crystallite size of the crystalline phase of Ce _x Zr _1-x O ₂ in a plane (111) is in a range from 1 nm to 50 nm. According to the catalyst described above, it is possible to steadily convert tar-containing gases generated by thermally decomposing coal or biomass into a light chemical substance, such as carbon monoxide or hydrogen. In particular, it is possible to convert even tar-containing gases that contain a high concentration of hydrogen sulfide into a light chemical substance, such as carbon monoxide or hydrogen, by bringing the tar-containing gas in contact with the catalyst without perform a desulfurization treatment, in order to reform tar in the crude gas or reform a hydrocarbon component in the purified gas.
[00261] Furthermore, another specific example of the catalyst that can preferably be used in the continuous fixed bed reactor of the modality is a catalyst to reform tar-containing gases, that is, a complex oxide represented by aM ^ bNLcMg ^ dO in which a, and b and c satisfy a + b + c = 1, 0.02 <a <0.98, 0.01 <b <0.97 and 0.01 <c <0.97, d represents a value in which oxygen and a positive element becomes electrically neutral, and M represents at least one element selected from Li, Na and K (Japanese Patent Unexamined Application, First Publication No. 2011-212552, Japanese Patent Unexamined Application, First Publication No. 2011-212552, and Japanese Patent Unexamined, First Publication No. 2011-212598). A preferred example of a complex oxide is a complex oxide formed by adding at least one oxide selected from silica, alumina and zeolite in which, in addition, the amount of at least one oxide selected from silica, alumina and zeolite is preferably in a range of 1 % by mass to 90% by mass in relation to the whole of the complex oxide. According to the catalyst described above, it is possible to steadily convert gases containing al
77/137 cages generated by thermally decomposing coal or biomass into a light chemical substance, such as carbon monoxide or hydrogen. In particular, it is possible to convert even tar-containing gases that contain a high concentration of hydrogen sulfide into a light chemical substance, such as carbon monoxide or hydrogen, by bringing the tar-containing gas in contact with the catalyst without perform a desulfurization treatment, in order to reform tar in the crude gas or reform a hydrocarbon component in the purified gas.
Effect of limiting the type of the catalyst to the tar reforming catalyst [00262] In the past, the reason for the blockage in the catalyst retainer was unclear. Generally, there were many cases where the catalyst retainer was provided in the upper section of the catalytic layer (the lower section of the catalytic layer was supported by the catalyst retainer, and raw gas material was supplied from below. So the influx of dust coarse gas raw material into the catalytic layer could be avoided, which makes this layout preferable), and when the catalyst retainer was blocked, it was considered that the block in the catalyst retainer resulted from the flow of dust from of the upper stream, such as coal dust, or the fact that tar in the form of mist, generated in the upper stream, had been attached to the catalyst retainer, and the tar had been transformed into a high melting point hydrocarbon, which that would cause the block. That is, it was considered that the blockage in the catalyst retainer resulted not from the catalyst, but from the raw gas material.
[00263] However, as a result of extensive investigation by the inventors, it was clarified that the product of a tar reforming reaction with the use of a catalytic layer that was the
78/137 series of catalyst types described above, was a mixture of approximately 70% or more of amorphous carbon (solid carbon) and solid hydrocarbon such as coke. Generally, dust in the raw gas material rarely contains amorphous carbon, and under the temperature condition of less than 900 ° C as in the reform reaction reaction test described above, there is little chance of the tar in the form of mist becoming amorphous carbon without contacting the catalyst. Therefore, it was clarified that the old description was not true, and that the blockage in the catalyst retainer resulted from the catalytic reaction. As a result of further investigation of the physical properties of the solid mixture, it has been found that a catalyst made from the material described above has a relatively low surface-fastening property of the catalyst. In addition, since the tar reforming performance is extremely favorable in the tar reforming reaction in which the catalyst described above is used, the amount of coke generated according to the reforming reaction is also extremely large compared to reform for which other methods are used. Therefore, in the tar reforming reaction in which the catalyst described above is used, since at least part of the solid mixture is separated from the catalyst surface and is compensated within the catalyst retainer and the like due to the force of gravity or action of the air stream, it has been found that when the catalyst retainer of the related technique is used in the tar reform reaction where the catalyst described above is used, the catalyst retainer is easily blocked.
[00264] According to the modality, a high orifice ratio and a mutually coupled opening shape are performed, and when applied to this type of catalytic reaction, there is an excellent effect that it is possible to reduce the adverse influence on the product ventilation
79/137 solid, which can be separated from the catalyst surface, and be compensated within the catalyst retainer during the reaction. Other applicable examples [00265] The modality may preferably be used in the following catalytic reactor in which the coking or similar occurs in addition to the continuous fixed bed reactor and catalyst exemplified above. [00266] 1) Methane reforming catalytic reactor: Comparative
Examples in Japanese Patent Unexamined, First Publication No. 2006-35172 discloses that a large amount of coking (carbon precipitation) occurs using methane gas, which is a hydrocarbon gas as raw material.
[00267] 2) Commercially available gas reforming catalytic reactor: Patent Document 2 describes examples of coking.
[00268] 3) Additionally, the invention can be applied to a catalytic reactor to reform a variety of purified petroleum gases such as LPG or natural gas, a catalytic reactor for a supply battery in which the gas containing hydrogen and an oxidizer gas are made to act, which thereby generates power and water as a by-product (for example, Japanese Patent Unexamined Application, First Publication No. 2009-48797), and the like. Fifth embodiment [00269] The continuous fixed bed reactor of the invention is not limited to the example illustrated in FIGS. 8A, 8B, 8C and 8D, and may have a catalytic retainer and catalytic layer arrangement as shown in FIG. 12.
[00270] In the present example, although reference numerals represent the same members as in FIGS. 8A, 8B, 8C and 8D, the catalytic reaction container 211 has inflow tube 213 for raw gas material 216 and efflux tube 214 for reformed gas 217
80/137 on both side surfaces in the upper section of the catalytic reaction container 211, and the catalyst retainers 218 are arranged on both side surfaces of the catalytic reaction container 211 in order to maintain the catalyst on the side surfaces. The catalyst retainer 218 can have the same structure as shown in FIG. 9. The crude gas material 216 flows into the catalyst 212 retained by the catalyst retainers 218 through spaces between the pins in the catalyst retainer 218 (left) as flow paths from the inflow tube 213. The reformed gas reacted and generated using catalyst 212 in the catalytic reaction container 211 flows into the efflux tube 214 through spaces between pins 218 in catalyst retainer 218 (on the right), which retains catalyst 212 as flow paths , and is expelled out.
Sixth modality [00271] There are cases where a part of a solid or liquid product generated from the catalyst reaction is separated from the catalyst surface, is dropped or transported to the downstream side of the main stream, and is accumulated in the spaces between the pins on the catalyst retainer provided on the side downstream of the main chain, which thus makes ventilation between the pins difficult. Therefore, a storage space can be provided in the lower section of the catalytic reaction container, or in the section downstream of the main stream, to compensate for the solid or liquid product separated from the catalyst surface.
[00272] FIGS. 13A, 13B and 13C illustrate an example of storage space. FIG. 13B is a cross-sectional view of a front surface of the continuous fixed bed reactor, FIG. 13A is a cross-sectional view A-A of FIG. 13B, and FIG. 13C is a cross-sectional view B-B of FIG. 13B. Although the basic configuration of the continuous fixed bed reactor is the same as that of the fixed bed reactor
81/137 shown in FIGS. 8A, 8B, 8C and 8D, in this example, the inflow tube and the efflux tube are installed in the top and bottom sections (the top surface and the bottom surface) of the catalytic reaction container 211. On the bottom side ( the bottom surface) of the catalytic reaction container 211, for example, catalyst retainer 218 is installed in a round tube 222 larger than catalyst retainer 218, in order to allow a reaction by-product dropped into the catalyst retainer 218 additionally drop into a space 223 below the side section of the catalyst retainer 218, and the space below the catalyst retainer 218 formed by the round tube 222 can be used as the storage space 223. In FIGS. 13A and 13B, reference numeral 225 represents a fallen substance. Round tube 222 is used as a part of the inflow tube. The member that forms the storage space is not limited to the round tube. In addition, in the continuous fixed bed reactor illustrated in FIGS. 13B and 13C, for example, an up and down movement apparatus 316 as described in an embodiment that will be subsequently described, and a driving geometry axis 317 that connects the up and down movement apparatus 316 to the catalyst retainer , can be installed.
[00273] At that time, a skylight 224 can be additionally provided above the storage device 223 as illustrated in FIGS. 14A, 14B and 14C, which in this way prevents the re-diffusion of the compensated product. In the continuous fixed bed reactor illustrated in FIGS. 14B and 14C as well as, for example, the up and down movement apparatus 316 as described in an embodiment that will subsequently be described, and the driving geometry axis 317 that connects the up and down movement apparatus 316 to the retainer catalyst, can be installed.
Catalytic Reaction Method
82/137 [00274] In the continuous fixed bed reactor and in the catalytic reaction method of the invention, the type of catalytic reaction is not particularly limited. Preferred examples of the subject of the continuous fixed bed reactor of the invention include a method for reforming tar-containing gases with the use of the tar-containing gas reactor catalyst as described above. An example of this is a catalytic reaction in which hydrogen, carbon dioxide and water vapor in a tar containing gas generated by thermally decomposing a raw carbonaceous material are brought into contact with the tar containing gas reforming catalyst described above in the presence of the catalyst or in the presence of the reduced catalyst, which thereby reforms and therefore gasifies the tar-containing gas.
[00275] In addition, another example of this is a catalytic reaction in which at least any of hydrogen, carbon dioxide and water vapor is added to the tar-containing gas generated by thermally decomposing a raw carbonaceous material, in the presence of the catalyst of reforming of tar-containing gas or in the presence of reduced catalyst, which in this way reforms and therefore gasifies tar-containing gas.
[00276] Here, although the reaction path of the tar gasification reaction in which tar in the tar containing gas is gasified through catalytic reform is complex and inaccurate, it is considered that between tar and hydrogen in tar containing gas or hydrogen introduced from outside, for example, proceeds a displacement reaction to light hydrocarbon, which includes methane, through hydrogenolysis of a tar-condensed polycyclic aromatic element, as expressed in Formula 1. (Formula 1 describes a case where only methane is generated). In addition, between tar and carbon dioxide in gas containing tar, or carbon dioxide introduced from outside, a displacement reaction proceeds
83/137 hydrogen and carbon monoxide through dry reform using polycyclic aromatic carbon dioxide condenses into tar, as expressed in Formula 2. In addition, between tar and water vapor in tar-containing gas , or water vapor introduced from outside, proceeds with a steam reform and a displacement reaction in aqueous gas, as expressed in Formula 3. In addition, reactions proceed in the same way for hydrocarbon components other than tar in gas containing tar .
C _n H _m + (2n-m / 2) H2 ^ nCH4 (Formula 1)
C _n H _m + n / 2CO2 ^ nCO + m / 2H2 (Formula 2)
C _n H _m + 2nH2O ^ nCO2 + (m / 2 + n) H2 (Formula 3) [00277] Therefore, in a case where high BTU gas such as methane is produced, it is desirable to add hydrogen from outside. In addition, in a case where hydrogen or carbon monoxide is produced, it is desirable to add carbon dioxide from outside. In addition, in a case where a greater amount of hydrogen is produced, it is desirable to add water vapor from outside. In addition, reactions are also carried out according to Formulas 1 to 3 for hydrocarbon components other than tar.
[00278] Here, it is preferable to reduce the catalyst to reform tar-containing gases; however, since the catalyst is reduced during the reaction, the catalyst can remain unreduced. In a case where the tar-containing gas reforming catalyst is particularly required to be reduced before the reaction, the reaction conditions are not particularly limited, as long as the temperature is relatively high and the atmosphere is a reduced atmosphere, since nickel particles that are an active metal are precipitated in a fine grouping format from the catalyst. For example, the atmosphere can be a gaseous atmosphere that includes
84/137 at least any one of hydrogen, carbon monoxide and methane, a gaseous atmosphere obtained by mixing water vapor with the reducing gas described above, or an atmosphere obtained by mixing an inert gas such as nitrogen with the gas described above. In addition, the reduction temperature is preferably, for example, in a range of 500 ° C to 1000 ° C. The reduction time is dependent on an amount of the catalyst to be charged as well, and is preferably, for example, in a range of 30 minutes to 4 hours, but there is no particular limitation in this condition as long as the time is long enough to reduce all charged catalyst particles.
[00279] An inlet temperature of the catalytic layer in the catalytic reaction container is preferably in the range of 500 ° C to 1000 ° C. In a case in which the inlet temperature of the catalytic layer is less than 500 ° C, the activity of the catalyst is rarely exhibited when tar and hydrocarbon are reformed into light hydrocarbons that contain mainly hydrogen, carbon monoxide and methane, which it is not preferable. On the other hand, in a case where the inlet temperature of the catalytic layer exceeds 1000 ° C, a structure with thermal resistance is required so that the reforming apparatus becomes expensive, which is economically disadvantageous. In addition, the inlet temperature of the catalytic layer is most preferably in the range of 550 ° C to 1000 ° C. In addition, it is also possible to progress the reaction at a relatively high temperature in a case where the carbonaceous crude material is silica, and at a relatively low temperature in a case where the carbonaceous crude material is biomass.
[00280] Here, even when the tar containing gas generated from thermal decomposition or partial oxidation of the raw carbonaceous material is tar containing gas that has a concentration
85/137 extremely high hydrogen sulfide, such as crude COG expelled from a coke oven, it is also possible to reform and gasify tar or hydrocarbon in the gas. In addition, the tar-containing gas described above can be transformed into a useful substance, in addition to being used for fuel use as in the related technique, and the tar-containing gas can be transformed into synthetic gas suitable for direct ingot reduction. iron, which can lead to a greater degree of energy use.
[00281] According to the continuous fixed bed reactor of the modality, even in a continuous fixed bed catalytic reaction that has a concern that the catalytic reaction container (particularly, between the catalyst particles, the catalyst) may be blocked due to to a solid by-product such as by the tar-containing gas reforming reaction, since the orifice ratio is significantly high compared to the catalyst retainer where puncture metal or a related art network is used, fluid resistance is low so that the operating cost is low and blocking the catalyst retainer by a solid by-product can be substantially avoided and therefore the catalyst retainer is washed if necessary only when the catalyst is washed to resolve the catalyst lock , and therefore it is possible to avoid stopping the operation of the continuous reactor to wash the catalyst retainer according to the related technique.
[00282] According to the modalities described above, a continuous fixed bed reactor that performs both a high orifice ratio and the prevention of blockage in the catalyst retainer, is provided. In addition, since it is possible to reduce the ventilation resistance of the catalyst retainer, ventilation into the catalytic layer is possible with only a small blowing force. In addition, it is possible to reform tar containing gases highly
86/137 efficient with the use of the continuous fixed bed reactor described above.
From the seventh to the ninth modality [00283] Next, from the seventh to the ninth modality of the invention will be described in detail with reference to the attached drawings. Meanwhile, in the description and drawings below, components that have substantially the same function will be provided with the same numerical references, and their duplicate description will not be made.
Seventh modality
General structure [00284] FIGS. 15A, 15B and 15C illustrate a continuous fixed bed reactor 310 according to the seventh embodiment of the invention. FIG. 15A is a plan view, FIG. 15B is a front view, and FIG. 15C is a side view. The continuous fixed bed reactor 310 of the present embodiment includes a reaction container 311, and the reaction container accommodates a catalyst bar 314, which is a series collection of catalyst particles 313 retained by a retention plate 312.
[00285] As described above, the feature of the modality is the use of the catalyst particle series 313 and the catalyst bar 314, which is a collection of the catalyst particle series. The series of catalyst particles 313 is formed from a plurality of catalyst particles 351 and a central rod 352 that penetrates the catalyst particles without disrupting the mobility of the catalyst particles to form the series of catalyst particles as illustrated in FIGS. . 19A and 19B. The catalyst bar 314 is formed of a plurality of the series of catalyst particles 313 and the retaining plate 312 which installs the central rods 352 upright, i.e., fixes the central rods in a standing state as illustrated in FIGS. 20A and 20B. In the seventh embodiment illustrated in FIGS. 15A, 15B and 15C, collars 322 are arranged between the retaining plate 312 and
87/137 the series of catalyst particles 313.
[00286] Another feature of the modality is that the drive mechanism 315, to move the catalyst bar reciprocally in the vertical direction when moving the retaining plate up and down, is installed below the retaining plate 312. The driving mechanism
315 is configured from the up and down motion apparatus
316 and the driving geometry axis 317 connects the up and down movement apparatus 316 to the retaining plate 312.
[00287] In reaction container 311, the crude gas material 318 is supplied from the bottom section, it is reacted when the main stream of the crude gas material passes through the catalyst bar 314 in parallel with the series of catalyst particles 313, and the reformed gas 319 from the catalytic layer 314 is expelled through the upper section of the reaction container 311. Examples of the crude gas material 318 include hydrocarbon-containing gas, tar and hydrocarbon-containing gas, and the like. Examples of reformed gas 319 include reformed gas obtained by reforming hydrocarbon-containing gases, and the like. Examples of the catalyst include a catalyst to reform hydrocarbons and the like, and a solid substance, for example, solid carbon or the like, is accumulated on the surface of the catalyst as a by-product of the catalytic reaction. In a case in which the catalytic reaction is an endothermic reaction, the temperature and heat required for the reaction can be supplied by arranging the catalytic reaction container 311 in, for example, a heating furnace (not shown). In a case where the catalytic reaction is an exothermic reaction, the heat of the reaction can be removed by making a cooler flow through a coolant flow path (not shown) provided outside the catalytic reaction container. Depending on cases, the raw gas material can be supplied to reaction container 311 in order to flow from the top side to the side
88/137 from the bottom of the catalyst bar 314, which is the opposite of the flow in FIGS. 15A, 15B and 15C.
Reaction container format [00288] Reaction container 311 can have any shape as long as the reaction container has openings 320a and 321a and is capable of storing the catalyst bar in a space between the openings. Opening 320a is communicated to a supply tube and thus sets up an inflow path 320 for a catalytic reaction fluid (raw gas material), and is equivalent to an inflow opening of reaction container 311 for the catalytic reaction fluid . Opening 321a is communicated to an exhaust pipe and thus sets up an efflux path 321 for reformed gas from reaction container 311, and is equivalent to an outflow opening of reaction container 311 for reformed gas. Reaction container 311 can have, for example, a cylindrical shape, a rectangular duct shape, or the like, and hereinafter, a rectangular duct shape reaction container will be described as an example.
[00289] In the following description, the central geometric axis of the container is defined as a geometric axis that connects the centers of the horizontal cross-sectional views of the container in series in the perpendicular direction. The reaction container thickness is equivalent to the minimum length of the typical reaction container lengths in a horizontal cross-section, and the width of the reaction container is equivalent to the maximum length of the typical reaction container lengths in a horizontal plane. In a case where the container is a cylinder, the width and thickness of the container can be replaced by the diameter.
Material for the reaction container [00290] Any material can be used as the material of the reaction container 311, as long as the material has a great strength o
89/137 sufficient to maintain the thermal resistance and corrosion resistance of the catalyst against a fluid that participates in the catalytic reaction, and the resistance to contamination against a reaction product. Examples of the material that can be used include metallic materials such as carbon steel, stainless steel, a nickel alloy, copper, a copper alloy, aluminum, an aluminum alloy, titanium and a titanium alloy; ceramic materials (which include ceramic materials processed into bricks) such as silica, alumina, silicon nitride and silicon carbide; and glass materials such as sodium glass and fused silica.
Reaction container dimensions [00291] Both the reaction container thickness and the reaction container width are required to be greater than the catalyst diameter. When the reaction container is thick, a large amount of the catalyst can be accommodated in the reaction container catalyst using space efficiently. In general, in the catalytic reaction, since heat is generated or absorbed and heat is communicated to the outside through the surface of the reaction container, it becomes more difficult to transfer in the thickness direction depending on the thickness of the reaction container. increases. Therefore, the thickness (the diameter in a case where the reaction container has a round cross section) of the reaction container is preferably 500 mm or less. In addition, it is not necessary to mention, the thickness of the reaction container is required to be greater than the typical dimension (for example, the diameter of the catalyst) of the catalyst being accommodated.
[00292] There is no particular limitation with the width of the reaction container in terms of function. The width can be determined from an engineering point of view based on the volume of the catalyst layer to be retained and the thickness of the reaction container taking into account structural and strength limitations (eg 5,000
90/137 mm).
[00293] The height of the reaction container is required to be equal to or greater than the height of the series of catalyst particles when moved upwards. In the meantime, there is no particular limitation on the height of the reaction container in terms of function and can be determined from an engineering point of view taking into account structural and strength limitations (eg 5,000 mm).
Catalyst particle series and catalyst bar [00294] As illustrated in FIGS. 19A and 19B, the series of catalyst particles 313 is configured of catalyst particles 351 which have a bore in the cylindrical or similar inner side and a central rod 352 which penetrates a group of the catalyst particles 351. As illustrated in FIGS. 20A and 20B, the catalyst bar 314 is produced by attaching a group of the catalyst particle series 313 to the retention plate 312.
[00295] In a case where the catalyst bar 314 is arranged in the reaction container 311 so that the series of catalyst particles 313 is along the vertical direction as illustrated in FIGS. 15A, 15B and 15C, it is possible to provide collars to prevent collars 322 (FIGS. 15A, 15B and 15C) from being loosened in the bottom section (portions where the series of catalyst particles and the retaining plate are joined ) of the central rods 352. Loosening of the catalyst particles can be prevented by providing the collar 322 with a diameter larger than the diameter of the bore catalyst. In addition, in this case, a space below the collars 322 serves as a space for the inflow and outflow of a fluid and a space in which the product generated on the catalyst surface is released and accumulated.
[00296] In a case where the catalyst bar 314 is arranged in the reaction container 311 so that the series of catalyst particles 313 are along the horizontal direction as in an octave
91/137 modality that will subsequently be described, both ends of the central rod 352 are joined to the retaining plate 312. Catalyst bar orifice ratio [00297] The catalyst bar orifice ratio can be defined as the orifice ratio = (1- [the cross-sectional area of a cross-section perpendicular to the main catalyst bar stream] / [the apparent cross-sectional area in a direction perpendicular to the main stream of the catalytic reaction container]) x100 (%). The main stream is defined as a flow of a fluid supplied to the reaction container 311 which moves from the inflow opening 320a to the outflow opening 320b in the reaction container 311 and in the case of FIGS. 15A, 15B and 15C, the main stream is the flow of a fluid in a direction parallel to the series of catalyst particles 313. As the orifice ratio of the catalyst bar increases, resistance to ventilation decreases. Meanwhile, when the orifice ratio is excessive, the required volume of the catalytic reaction container increases and the resistance to ventilation is small and therefore leakage is likely to occur. Therefore, the orifice ratio is preferably in the range of 30% to 60%.
Central stem in the Catalyst Particle Series [00298] The central stem in the catalyst particle series is preferably a round stem since the round stem can penetrate the catalyst particles without causing damage to the catalyst particle series. However, for the sake of processing convenience and the like, the central stem may be a stem that has a polygonal cross-section.
[00299] In addition, the central rod preferably has a linear shape to allow the catalyst particles to move around the central rod. However, for the sake of processing convenience, the central stem may be a curved stem.
92/137 [00300] The diameter of the central rod is required to be less than the bore diameter of the catalyst. In addition, the central rod preferably has an appropriate diameter to have a force large enough to retain the catalyst or withstand the up and down movement and to prevent buckling caused by creep and the like at a high temperature. For example, a diameter in a range from 1 mm to 30 mm can be applied.
[00301] As a material for the central rod, metal, particularly stainless steel, a nickel alloy such as INCONEL (trademark), titanium or a titanium alloy can be used from the point of view of strength, rigidity, thermal resistance and the like and for a reason that a material with a high thermal conductivity is preferred. In addition, copper, a copper alloy, aluminum, an aluminum alloy and the like are particularly preferred as the material with a high thermal conductivity.
Length of the Catalyst Particle Series [00302] There is no particular limitation on the length of the catalyst particle series as long as the catalyst bar that moves reciprocally in the vertical direction can be accommodated in the reaction container and the length of the series of catalyst particles catalyst is in a range of the height of the catalytic reaction container. The length of the series of catalyst particles can be freely determined by increasing the number of catalyst particles penetrated by the central rod. However, in the case of a series of long catalyst particles, since the concentration of the raw material fluid on the downstream side, the reaction rate of the catalytic reaction decreases. Therefore, the ideal length needs to be appropriately determined taking into account the ratio between the flow rate of the raw material fluid to be treated and the total amount of the catalyst.
Production method of the catalyst particle series
93/137 [00303] The series of catalyst particles can be produced by manually penetrating the central rod through the catalyst particles.
Retention plate of the catalyst particle series [00304] The retention plate that supports the catalyst particle series is produced using a material that allows the fixation of the central rod with a welding method, screwing or similar. A material for the retaining plate can be, similar to the central rod, stainless steel, a nickel alloy such as INCONEL (registered trademark), titanium, a titanium alloy or similar from the point of view of strength, rigidity, strength thermal and the like. In a case where the collars are used, it is also possible to produce the collars using the same material for the retaining plate. Catalyst bar drive mechanism [00305] In the embodiment, the retaining plate 312 is moved up and down, thus moving the catalyst bar 314 on the retaining plate up and down in the reaction container 311 To move the retaining plate up and down, the drive mechanism 315 that moves the retaining plate 312 up and down is mounted on the reaction container 311 of the embodiment. As the drive mechanism 315, it is possible to use a common drive mechanism such as a compressed air cylinder or the up and down movement apparatus 316 in which a gear such as a rack and pinion is used. The retaining plate 312 is coupled to the up and down movement apparatus 316 using the driving axis 317. When the up and down movement apparatus 316 is operated, the entire retaining plate 312 is moved along of the axial line of the reaction container 311, thus moving the entire catalyst bar 314 up and down along the axial line of the reaction container
94/137
311 as well.
[00306] At least a portion of the driving geometry axis 317 on the side of the retaining plate 312 is required to be inside the reaction container 311 or the raw material inflow path 320 or the reformed gas efflux path 321 which can be present in the bottom section of the reaction container 311. The up and down movement apparatus 316 can be provided on the outside of the reaction container 311. In a case where the reaction container 311 is arranged in a heating (not shown) like a heating oven, it is also possible to supply the up and down movement apparatus 316 on the outside of the heating apparatus. In that case, a commercially available up and down motion apparatus may be used, and it is necessary to seal a portion in which the driving geometry axis 317 penetrates the reaction container 311 through the packaging for use at high temperature.
[00307] In a case where the entire drive mechanism 315 is provided in the reaction container 311 as illustrated in FIGS. 15A, 15B and 15C, the up and down movement apparatus 316 is required to have thermal resistance and corrosion resistance to protect the up and down movement apparatus 316 from, for example, a high temperature or corrosive substance in the container reaction 311. What has been described above can be accomplished by, as an example, producing the entire compressed air cylinder of the 315 drive mechanism using a thermally resistant metal alloy such as HASTELLOY (trademark). In this case, an air supply tube (not shown) to the compressed air cylinder penetrates the reaction container 311; however, since the air supply tube is an immobile section, the air supply tube can be sealed by welding the entire circumference of the tube.
95/137
Up and down stroke of the retaining plate [00308] To make the catalyst particles move sufficiently more relative to each other, the up and down stroke of the retaining plate 312 is preferably large. For example, even at an up and down stroke of approximately 10% of the typical dimension (eg, diameter) of the external catalyst surface, a vibration effect can be obtained and, therefore, a degree of an effect that removes the substance accumulated on the catalyst surface such as solid carbon can be obtained. However, in order to obtain a sufficient accumulated substance removal effect, the up and down stroke of the retaining plate 312 is preferably 50% or more and more preferably 100% or more of the typical dimension of the external catalyst surface.
[00309] Meanwhile, in a case where the up and down stroke is extremely large, an increase in the sizes of the reaction container 311 and the drive mechanism 315 is caused, which is not efficient. In addition, repeating the up and down motion with a small stroke (100% or more) also produces the same effect as a large up and down stroke. Therefore, the up and down stroke is preferably 1,000% or less of the typical dimension of the external catalyst surface.
Movement speed up and down of the retaining plate [00310] There is no particular limitation with the speed in elevation. The rate of reduction needs to be established to enable sufficient relative movement between the catalyst particles to separate the solid accumulated substance from the catalyst surface. At an extremely reduced speed, the catalyst particles do not move relative to each other, which is not preferred. The reduction rate can be set to be less than the free fall rate of the catalyst particles (e.g.
96/137 (example, 100 mm / s). Therefore, the speeds in reduction of the catalyst particles vary depending on the contact state between the catalyst particles and the central rod when individual catalyst particles decrease and it is possible to cause relative movement and collision between the catalyst particles.
[00311] Alternatively, when the speed of the central rod is made to be less than the speed of the catalyst particles in the terminal portion of the reciprocal movement by the drive mechanism, it is also possible to supply an impact causing the catalyst particles to collide with the retaining plate with inertia. This method is particularly effective in a case where the catalyst bar is moved in the horizontal direction as in the eighth embodiment which will subsequently be described with reference to FIGS. 16A, 16B and 16C.
Catalyst particle shape [00312] It is necessary to prevent the catalyst particles from being released from the series of catalyst particles. Therefore, the catalyst particle advantageously has a shape that has a hole that allows the penetration of the central rod. For example, a catalyst particle that has a ring shape, a cylindrical shape, a duct shape or the like can be used. In addition, the catalyst particles may have a shape similar to a horseshoe that has an opening width less than the diameter of the central rod as a shape that satisfies the requirement to prevent the release of the catalyst particles.
[00313] The bore size of the catalyst particle is required to be sufficiently larger than the diameter of the central rod so that the catalyst particle has the ability to move freely against the central rod. Particularly, in a case where the series of catalyst particles is arranged horizontally and the vane bar
97/137 lyser moves reciprocally in the perpendicular direction as in the eighth modality that will be described subsequently, since the relative movement distance (in relation to the central rod) of individual catalyst particles in the perpendicular direction is limited to a range of [hole diameter central] - [central stem diameter], it is preferable to establish this difference to be large enough. For example, [center hole diameter] can be set to [center shank diameter] +1 mm.
Catalyst material and action [00314] The material or catalytic action of the catalyst to which the continuous continuous bed catalytic reactor of the modality can be applied is not particularly limited as long as the catalyst is a fluid, particularly a catalyst used in a reaction catalytic in which gas is used as a raw material. The continuous fixed bed catalytic reactor of the modality can preferably be used for a catalyst used in a catalytic reaction in which the fluid is gas and the products of the catalytic reaction are gas and a liquid or solid substance, preferably in a catalytic reaction in which the fluid catalytic reaction is gas containing hydrocarbon and the products of the catalytic reaction are gas and a liquid or solid substance and particularly in a catalytic reaction in which the fluid catalytic reaction is gas containing tar and the products of the catalytic reaction include solid hydrocarbon or carbon solid.
[00315] In general, the continuous fixed bed catalytic reactor of the modality can be widely used for an oxide catalyst used in the catalytic reaction described above and, particularly, it can be preferably used for an oxide catalyst used in the catalytic reaction in which the fluid catalytic reaction is tar-containing gas and the products of the catalytic reaction include solid hydrocarbon or solid carbon.
98/137 [00316] A specific example of the catalyst that can preferably be used in the continuous continuous bed catalytic reactor of the modality is a catalyst to reform tar containing gas which is an oxide containing nickel, magnesium, cerium and aluminum, includes at least less a complex oxide and does not include alumina as a single compound (WO2010 / 134326). A preferred example of the complex oxide is a complex oxide made of crystal phases of NiMgO, MgAl ₂ O ₄ and CeO ₂ , in which, in addition, in the respective crystal phases, the crystallite size of the NiMgO crystal phase in one ( 200) plane obtained from X-ray diffraction measurement is in a range from 1 nm to 50 nm, the crystallite size of the MgAl ₂ O ₄ crystal phase in a (311) plane is in a range of 1 nm to 50 nm, and the crystallite size of the CeO ₂ crystal phase in a (111) plane is in a range from 1 nm to 50 nm. The catalyst described above has a feature of an ability to convert even tar-containing gas that includes a large amount of hydrogen sulfide generated during the thermal decomposition of a crude material that contains carbon and mainly includes condensed polycyclic aromatic elements that are likely to cause precipitation of carbon in light hydrocarbon which mainly includes hydrogen, carbon monoxide and methane, highly and efficiently reforming the accompanying heavy hydrocarbon such as tar and a characteristic of, when the catalyst performance is deteriorated, removing precipitated carbon or sulfur adsorbed on the catalyst by placing it at least any one of water and air vapor in contact with the catalyst at a high temperature, thereby recovering the catalyst performance and enabling stable operation for a long period of time.
[00317] In addition, another specific example of the catalyst that can be preferably used in the fixed bed catalytic reactor
99/137 continuous mode is a catalyst for reforming tar - containing gas that is made of a complex oxide containing nickel, magnesium, cerium, zirconium and aluminum (unexamined Patent Application No. JP 2011-212574). A preferred example of complex oxide is a complex oxide that includes crystal phases of NiMgO, MgAl ₂ O ₄ and Ce _x Zr _1-x O ₂ (0 <x <1), where, in addition, in the respective crystal phases, the crystallite size of the NiMgO crystal phase in a (220) plane obtained from an X-ray diffraction measurement is in a range from 1 nm to 50 nm, the crystallite size of the MgAl ₂ crystal phase The ₄ in one (311) plane is in a range from 1 nm to 50 nm, and the crystallite size of the crystal phase of Ce _x Zr _1-x O ₂ in a (111) plane is in a range of 1 nm at 50 nm. According to the catalyst described above, it is possible to steadily convert tar containing gas generated when thermally decomposing silica or biomass into a light chemical substance such as hydrogen. In particular, it is possible to steadily convert even tar containing gas containing a high concentration of hydrogen sulphide into a light chemical substance such as carbon monoxide or hydrogen by placing the tar containing gas in contact with the catalyst without performing a desulfurization treatment in order to carry out the tar in the crude gas or carry out a hydrocarbon component in the purified gas.
[00318] Additionally, another specific example of the catalyst that can preferably be used in the continuous continuous bed catalytic reactor of the modality is a tar reform gas catalyst which is a complex oxide represented by aM ^ bNLcMg ^ dO in which a, b and c satisfy a + b + c = 1, 0.02 <a <0.98, 0.01 <b <0.97 and 0.01 <c <0.97, d represents a value where oxygen and an element positive become electrically neutral and M represents at least one element selected from Li, Na and K (Request for
100/137
Unexamined Patent, First Publication No. JP 2011-212552, Unexamined Patent Application, First Publication No. 2011212552 and JP Unexamined Patent Application, First Publication No. JP 2011-212598). A preferred example of the complex oxide is a complex oxide formed by adding at least one oxide selected from silica, alumina and zeolite, in which, in addition, the amount of at least one oxide selected from silica, alumina and zeolite is preferably in a range from 1% by mass to 90% by weight in relation to all complex oxides. According to the catalyst described above, it is possible to steadily convert tar containing gas generated when thermally decomposing coal or biomass into a light chemical substance such as carbon monoxide or hydrogen. In particular, it is possible to steadily convert even tar containing gas containing a high concentration of hydrogen sulphide into a light chemical substance such as carbon monoxide or hydrogen by placing the tar containing gas in contact with the catalyst without performing a desulfurization treatment in order to reform tar in the crude gas or reform a hydrocarbon component in the purified gas. Other applicable examples [00319] The invention can preferably be used in the following continuous fixed bed catalytic reactor in which coking or the like occurs in addition to the continuous fixed bed catalytic reactor and catalyst exemplified above.
[00320] 1) methane reforming catalytic reactor: Comparative Examples in Unexamined Patent Application, First Publication No. JP 2006-35172 discloses that a great number of coking (carbon precipitation) occurs with the use of methane as hydrocarbon which is raw material gas.
[00321] 2) Commercially available gas reform catalytic reactor
101/137 available: Patent Document 2 describes examples of coking.
[00322] 3) Additionally, the invention can be applied to a catalytic reactor for reforming a variety of purified petroleum gases such as LPG or natural gas, a catalytic reactor for a fuel cell in which the gas containing hydrogen and an oxidizer gas are made to act, thus generating, power and water as a by-product (for example, unexamined Patent Application, First Publication No. JP 2009-48797) and the like.
Eighth modality [00323] Next, a continuous fixed bed catalytic reactor according to an eighth modality will be described with reference to FIGS. 16A, 16B and 16C. FIG. 16A is a plan view, FIG. 16B is a front view and FIG. 16C is a side view. The continuous fixed bed catalytic reactor 310 in FIGS. 16A, 16B and 16C is the same as the continuous fixed bed catalytic reactor of the seventh embodiment described with reference to FIGS. 15A, 15B and 15C except that the catalyst bar is arranged in the reaction container so that the series of catalyst particles are along the horizontal direction.
[00324] In the present embodiment, the catalyst bar is formed by attaching both ends of the series of catalyst particles to the retention plate 312. It is not necessary to supply the collars used in the catalyst bar of the seventh mode in the joining portions between the series of catalyst particles and the retaining plate 312. The retaining plate 312 extends towards the bottom of a catalyst bar 314 ', is connected to a support member 325, and the support member 325 is coupled to the geometrical driving axis 317 in the up and down movement mechanism 315.
[00325] The eighth modality has the following characteristics.
[00326] (1) the catalyst bar is arranged in the reaction container
102/137 so that the series of catalyst particles is along the horizontal direction, that is, the series of catalyst particles are arranged in an orthogonal way to cross the main stream. In particular, the series of catalyst particles can be arranged in a zigzag format when viewed from the main stream. Then, the flow of the main stream collides with the catalyst surface which is the side surface of the series of catalyst particles and the flow orientation is bent so as to pass through both sides of the series of catalyst particles. At that time, a strong advection flow and a strong turbulent flow spread in a direction perpendicular to the main stream, thereby accelerating mass transfer and thermal migration in a direction perpendicular to the main stream. As a result, the amount of heat supplied to the outer reaction container surface in a case where the inner side of the reaction container is heated is carried deep into the reaction container and even when the catalytic reaction rate differs in the direction thickness of the reaction container, the concentration of the fluid in the thickness direction becomes uniform due to the effect of material transport and leakage is not easily caused. Particularly, in a case where the series of catalyst particles is arranged in a zigzag format, since the flow of the main stream is continuously doubled due to collision with the series of catalyst particles, mass transfer and thermal migration in the direction in thickness are additionally accelerated and the effects described above become more significant.
[00327] (2) It is possible to move reciprocally move the catalyst bar in the vertical direction. Therefore, the internal holes of the respective catalyst particles and the central rod are made to move in relation to each other to collide with each other. The use of vibration
103/137 runs during the collision enables the detachment and removal of the bulky solid product on the surfaces of the respective catalyst particles.
[00328] (3) It is possible to couple the central rods for the respective series of catalyst particles to the retaining plate that holds the catalyst bar and to heat the entire retaining plate through thermal conduction of the catalytic reaction container. Then, the thermal conduction between the retaining plate and the central rods for the series of catalyst particles is accelerated, and it is possible to heat the catalyst particles present in a region away from the reaction container wall through thermal conduction by the central rods. in contact with the catalyst particles since the retaining plate is retained at a high temperature at all times.
[00329] (4) It is also possible to reciprocally move the catalyst bar horizontally by providing a drive device to reciprocally move the catalyst bar in the horizontal direction. Then, similar to the seventh modality, the bulky solid product generated on the surfaces of the respective catalyst particles can be detached and removed causing the collision between the catalyst particles.
Ninth modality [00330] Next, a continuous fixed bed catalytic reactor according to a ninth modality will be described with reference to FIG. 17. A continuous fixed bed catalytic reactor 310 of FIG. 17 is the same as the continuous fixed bed catalytic reactor of the seventh embodiment described with reference to FIGS. 15A, 15B and 15C except that a heating apparatus 331 is provided at the ends of the series of catalyst particles.
[00331] The heating device 331 is provided between collars 322 below the series of catalyst particles 313 and the
104/137 retention 312, whereby it is possible to heat the central rods by wrapping a heating element (not shown) such as a nickel wire around the central rod, and heating the central rods by applying electricity. Electricity can be supplied to the heating element using a 332 electrical wire. The catalyst particles in the respective series of catalyst particles can be heated through the thermal conduction from the heated central rods in contact with the catalyst particles. A reforming reaction that accompanies an endothermic reaction can be carried out with high efficiency by heating the catalyst particles mainly through thermal conduction from the central rods.
[00332] The heating apparatus 331 can be supplied for the entire series of catalyst particles on the catalyst bar and can also be supplied for a part of the series of catalyst particles. Examples of the latter case include a case in which the heating apparatus is supplied for the series of catalyst particles in the central portion in the thickness direction of the reaction container. So, even in a reaction container that is very thick and needs heating from the outside through the wall, it is possible to sufficiently heat the catalyst particles in the central portion in the thickness direction of the reaction container where it is difficult to transfer enough heat from the outside.
[00333] In the invention, viable modalities are not limited to the modalities described above. For example, in the eighth embodiment, the series of catalyst particles can be arranged at an angle instead of being horizontally arranged. In the seventh and eighth modalities, the series of catalyst particles can be moved reciprocally in the horizontal direction. In addition, in the seventh and eighth modalities, the series of catalyst particles can be reciprocally
105/137 moved both in the perpendicular and in the horizontal direction. [00334] According to the continuous continuous bed catalytic reactor of the modality, it is possible to efficiently remove the solid accumulated substance that is generated and accumulated in the catalyst particles in the fixed bed catalyst layer in order to degrade the performance of the catalyst by moving it reciprocally the entire catalyst layer. Additionally, in the continuous fixed bed catalytic reactor according to the modality, since the series of adjacent catalyst particles is disposed at certain intervals in the catalytic reaction container, the blocking problem caused by the accumulation of the solid product in the spaces between the particles of catalyst generated in the catalyst layer and the like that is configured by randomly loading the catalyst is essentially avoided. Therefore, it is not necessary to interrupt the operation to wash the catalyst or catalyst retainer as in the related art, and it becomes possible to operate the reactor continuously. In addition, it is possible to cause with a high efficiency for a catalytic reaction that generates a solid product such as solid carbon using the continuous fixed bed catalytic reactor.
[00335] Until now, the invention has been described based on the first to ninth modalities, however the invention is not limited to the modalities described above and in the scope of the technical idea of the invention, a combination of the modalities described above can be used or part of configuration can be modified.
Examples [00336] The invention will be further described on the basis of the following test examples and reference examples. However, the invention is not limited to test examples and reference examples. Test Example 1-1 [00337] A test was performed using the apparatus illustrated in FIGS. 2A, 2B and 2C.
106/137
Configuration of the entire reaction system [00338] Coal-carbonized gas (which contains water vapor derived from moisture in the coal) was continuously generated by supplying coal to a calcination furnace heated from a coal supplier (quantity supplier coal hopper) at a rate of 20 kg / hour. An inflow opening in a continuous fixed bed catalytic reactor was connected to the calcination furnace using a heat retention tube, and an outflow opening in the continuous fixed bed catalytic reactor was connected to an induced draft fan via a scrubber using a heat retention tube. The tar in the carbonized gas by coal was reformed in the catalytic reaction container in order to generate light gas (hydrogen or similar), and the light gas was diffused as the reformed gas in the atmosphere through a torch chimney (which subjects the reformed gas) with the use of the induced draft fan. The catalytic reaction container was accommodated in an electric heating oven that has a controlled oven temperature at a constant temperature. The flow rate of the induced draft fan could be adjusted and was controlled at a flow rate that corresponds to the carbonized gas per coal generation rate.
Catalyst [00339] A catalyst that has a Ni ₀₁ Ce ₀₁ Mg ₀₈ O component system was used as the catalyst.
[00340] Nickel nitrate, cerium nitrate and magnesium nitrate were weighed so that the molar ratio of the metal elements became 1: 1: 8, nickel, magnesium and cerium were co-precipitated as hydroxides by adding an aqueous solution of potassium carbonate heated to 60 ° C to a mixed aqueous solution prepared at a heating temperature of 60 ° C and were sufficiently stirred using a stirrer. After that, nickel, magnesium and cel
107/137 rivers were aged and the agitation was continued for a certain period of time, while nickel, magnesium and cerium were retained at 60 ° C, so they were filtered by suction, and were sufficiently washed with pure water. (80 ° C). After the sedimentation obtained after washing was dried at 120 ° C and crushed coarsely, the crushed sediment was ignited (calcined) in the air at 600 ° C, crushed and then fed to a beaker. A sol alumina was added, the mixture was sufficiently mixed using a mixer equipped with a stirring blade and moved to an eggplant shaped jar. The eggplant-shaped flask was mounted on a rotary evaporator, and the mixture was sucked under stirring, thereby evaporating moisture. Nickel, magnesium, cerium and alumina compounds fixed to the wall surface of the flask in the shape of an eggplant were moved to an evaporation plate, dried at 120 ° C and calcined at 600 ° C. The powder was molded by pressure using a compression molder, thus producing a compact cylindrical that has an external diameter of 15 mm, an internal diameter of 5 mm and a height of 15 mm.
[00341] The compact was ignited in air at 950 ° C, and a catalyst compact was prepared by mixing 50% by weight of alumina with Ni ₀₁ Ce ₀₁ Mg ₀₈ O. As a result of the confirmation of the compact components through ICP analysis, it was confirmed that the compact had the desired components. In addition, as a result of measuring the compact using a kyia type hardness meter, it was observed that the compact retains a high strength of approximately 100 N.
Continuous fixed bed catalytic reactor [00342] The continuous fixed bed catalytic reactor used was as described below.
[00343] Reaction container format: a format duct in which the
108/137 cross section perpendicular to the central geometric axis had a rectangular shape and constant dimensions [00344] Reaction container material: stainless steel [00345] Reaction container thickness: 120 mm [00346] Reaction container width: 300 mm [00347] Catalyst layer height: 400 mm [00348] Aspect ratio of the catalyst layer: 3.3 [00349] Up and down stroke of the drive device: 15 mm [00350] Lifting speed of the drive device: 2 mm / second [00351] Reduction speed of the drive device: 100 mm / second [00352] Catalyst retainer: stainless steel round rod pin type catalyst retainer [00353] Pin: the height was 5.1 mm, the length was 90 mm, the top section was flat and the corner section was 1 mm face.
[00354] Pin layout: all pins have been welded to the bottom plate of the catalyst retainer in the shape of an isosceles triangle that has a bottom side of 16 mm (in the direction of reaction container width) and a height of 13.5 mm (on the thick side of the reaction container).
[00355] Pin orifice ratio: 92% [00356] Catalyst quantity used: 7 kg [00357] The catalyst described above was accommodated in the continuous fixed bed catalytic reactor illustrated in FIGS. 2A, 2B and 2C, and a thermocouple was inserted in the central position of the catalyst layer.
[00358] Before the start of a reform reaction, first, the reactor temperature was increased to 800 ° C in a nitrogen atmosphere, and a reduction treatment was performed for 30 minutes
109/137 while making hydrogen gas flow at 80 NI / min. After that, the coke oven gas was adjusted and introduced, and the reaction was evaluated at normal pressure.
[00359] Regarding the operation timing of the drive device, the first and second up and down movements were made respectively in three hours and four hours after the beginning of the carbonized gas ventilation by moving the layer reciprocally of catalyst twice.
Operating conditions [00360] The operating conditions were as described below. [00361] Temperature of the carbonized calcination furnace with coal: 750 ° C [00362] Temperature of the electric heating furnace: 800 ° C [00363] Flow rate of the carbonized gas by coal: 10 Nm ³ / h in an average [00364 ] Ventilation period of carbonized gas by coal: five hours
Results [00365] The test results were as described below.
[00366] Ventilation property (pressure loss) [00367] Immediately after ventilation starts: 0.1 kPa [00368] In the first up and down movement: 4 kPa (immediately before) ^ 0.3 kPa (immediately after) [00369] In the second up and down movement: 4 kPa (immediately before) ^ 1.0 kPa (immediately after) [00370] As described above, it was admitted that the ventilation property was recovered by the up and down movement of the catalyst layer.
[00371] Reform characteristics (hydrogen amplification rate = hydrogen flow rate in the reformed gas / hydrogen flow rate
110/137 hydrogen in the crude gas) [00372] Immediately after the start of ventilation: 3.5 [00373] In the first up and down movement: 2.5 (immediately before) ^ 2.3 (immediately after) [00374] In the second up and down movement: 1.8 (immediately before) ^ 1.7 (immediately after) [00375] As described above, in the present test example in which the aspect ratio of the catalyst layer was 3.3 (greater than two), it was observed that the recovery effect of reforming characteristic of the up and down movement of the catalyst layer was limited.
[00376] As a result of investigating the interior of the disassembled device after the end of the test, while 40 g of solid carbon was accumulated on the bottom plate of the retainer, on the surface of the retainer, only a thin film of solid carbon was generated, not bulky solid carbon was attached to the pins and the ventilation resistance of the retainer was the same as the resistance to ventilation when the retainer had been installed.
TEST EXAMPLE 1-2 [00377] A test was performed using an apparatus in which a catalytic reaction container not equipped with the drive mechanism of Test Example 1-1 (the catalyst retainer was attached) was used and a hammering device that periodically hits the side wall of the catalytic reaction container using a weight.
[00378] Regarding the operation timing of the hammering device, the first and second hammerings were done respectively in three hours and 3.5 hours after the beginning of the carbonized gas ventilation by moving the catalyst layer reciprocally ten times.
111/137 [00379] Other conditions were the same as in Test Example 1-1.
Results [00380] The test results were as described below.
[00381] Ventilation property (pressure loss) [00382] Immediately after ventilation starts: 0.1 kPa [00383] At the first hammering: 4 kPa (immediately before) ^ 2.5 kPa (immediately after) [00384] In the second hammering: 4 kPa (immediately before) ^ 4 kPa (immediately after) [00385] As described above, there was no effect of recovering hammering ventilation property in the second hammering and the effect of the first hammering was less, also, in the Test example 1-1. Since the pressure loss was not diminished, the catalyst layer was determined to be blocked and ventilation was stopped four hours after the start of ventilation.
TEST EXAMPLE 1-3 [00386] A test was performed in the same way as in Test Example 1-1 with the exception of the facts that the height of the catalyst layer was set at 150 mm, the weight of the catalyst was set at 2.5 kg, the volume ratio of the crude material gas (carbonized gas to coal) / catalyst was established to be the same as in Test Example 1-1, the drive device was established to have the following conditions, which are , [00387] Drive device up and down stroke: 20 mm [00388] Drive device lift speed: 2 mm / second [00389] Drive device reduction speed: 10 mm / second, and
112/137 [00390] Regarding the operation timing, the first and the second up and down movements were made respectively in three hours and five hours after the beginning of the ventilation of carbonized gas by coal moving the layer of reciprocating reciprocally. catalyst twice.
Results [00391] The test results were as described below.
[00392] Ventilation property (pressure loss) [00393] Immediately after ventilation starts: 0.1 kPa [00394] In the first up and down movement: 4 kPa (immediately before) ^ 0.25 kPa (immediately after) [00395] In the second up and down movement: 4 kPa (immediately before) ^ 0.6 kPa (immediately after) [00396] As described above, it was assumed that the ventilation property was recovered by the upward movement and below the catalyst layer.
[00397] Reform characteristics (hydrogen amplification rate = hydrogen flow rate in the reformed gas / hydrogen flow rate in the raw material gas) [00398] Immediately after the start of ventilation: 3.3 [00399] No first movement up and down: 2.4 (immediately before) ^ 2.8 (immediately after) [00400] In the second movement up and down: 1.4 (immediately before) ^ 2.0 (immediately after) [00401] As described above, in the present test example in which the aspect ratio of the catalyst layer was 1.25 (less than two), it was assumed that the catalyst reforming performance was recovered by the up and down motion low. This can be said to be the effect of the stirring ability of all the catalyst particles in the catalyst layer.
113/137 [00402] After the end of the test, while 70 g of solid carbon was accumulated in the bottom plate of the retainer, on the surface of the retainer, only a final film of solid carbon was generated, there was no fixation of solid carbon of shape bulky to the pins and the ventilation resistance of the retainer was the same as the ventilation resistance when the retainer was installed.
REFERENCE EXAMPLE 1-1 [00403] Nickel nitrate, cerium nitrate, zirconium oxide and magnesium nitrate were weighed so that the molar ratio of the metal elements became 1: 1: 1: 7, nickel, cerium, zirconium and magnesium were co-precipitated as hydroxides by adding an aqueous solution of potassium carbonate heated to 60 ° C to a mixed aqueous solution prepared at a heating temperature of 60 ° C, and were sufficiently stirred using a stirrer .
[00404] After that, nickel, cerium, zirconium and magnesium were aged, continuing to stir for a certain period of time while retaining nickel, cerium, zirconium and magnesium were at 60 ° C, so they were suction filtered, and were sufficiently washed with pure water (80 ° C). After the sedimentation obtained after washing was dried at 120 ° C and coarsely crushed, the crushed element was calcined in the air at 600 ° C, crushed and then fed to a beaker. A sol alumina was added, the mixture was sufficiently mixed using a mixer equipped with a stirring blade and moved to an eggplant shaped jar. The eggplant-shaped flask was mounted on a rotary evaporator, and the mixture was sucked under stirring, thereby evaporating moisture. Nickel, magnesium and alumina compounds attached to the wall surface of the jar in the shape of an eggplant were moved to an evaporation plate, dried at 120 ° C
114/137 and calcined at 600 ° C. Then, the powder was molded by pressure into a tablet format that has a diameter of 3 mm using a compression molder, thereby producing a tablet compact. The compact was ignited in air at 950 ° C, and a catalyst compact was prepared by mixing 50% by weight of alumina with Ni0.1Ce0.1Zr0.1Mg0.7O.
[00405] As a result of confirming the components of the compact through ICP analysis, it was confirmed that the compact had the desired components. In addition, as a result of an XRD measurement of the present prepared product, it was clarified that the prepared product was made from the phases of NiMgO, MgAl ₂ O ₄ and Ce _x Zr _1-x O ₂ , and the size of the respective crystallites were 14 nm, 11 nm and 22 nm.
[00406] The catalyst was fixed using a silica wool in order to be located in the center of a SUS reaction tube, a thermocouple was inserted in the central position of the catalyst layer, and the fixed bed reaction tube was established in a predetermined location.
[00407] Before the start of a reform reaction, firstly, the temperature of the reaction container was increased to 800 ° C in a nitrogen atmosphere, and a reduction treatment was carried out for 30 minutes at the same time as making gas of hydrogen flow at 100 ml / min. After that, coke oven stimulating gas (crude gas) (hydrogen: nitrogen = 1: 1, 2,000 ppm H2S was contained, and the total flow rate was 125 ml / min) was prepared and introduced into the reaction. In addition, as a tar-stimulating substance generated during carbonization of coal, 1-methyl naphthalene which was a liquid substance that was actually contained in tar and had a low viscosity at room temperature was introduced into the reaction container as a typical substance in a fee
115/137 flow of 0.025 g / min and was reacted at normal pressure.
[00408] As a result of collecting and observing the catalyst after the end of the test, a large amount of bulky shaped carbon was accumulated between the catalyst particles. As a result of sieving the catalyst particles and the accumulated substance, most of the bulky shaped carbon on the catalyst surface was separated from the catalyst surface due to several times fine vibration, passed through the openings in the sieve and released.
[00409] Therefore, it was observed that, in a case where the present catalyst was used, most of the solid carbon accumulated between the catalyst particles passed through the catalyst particles due to the slight agitation of the catalyst particles, and fell . Based on the result described above, it can be considered that when the apparatus of Test Example 1-1 or 1-3 is used in a reforming reaction in which the present catalyst is used, it is possible to significantly avoid fixing the product to the retention section of the catalyst layer and the lock in the catalyst layer.
REFERENCE EXAMPLE 1-2 [00410] Nickel, magnesium and sodium were weighed so that their atomic weights (%) became 10%, 80% and 10% respectively, nickel, magnesium and sodium were co-precipitated as hydroxides adding an aqueous solution of potassium carbonate heated to 60 ° C to a mixed aqueous solution prepared at a heating temperature of 60 ° C, and were sufficiently stirred using a stirrer. After that, nickel, magnesium and sodium were aged by continuing to stir for a period of time while retaining nickel, magnesium and sodium were at 60 ° C, so they were filtered with suction, and were sufficiently washed with use of pure water (80 ° C).
116/137 [00411] After the sedimentation obtained after washing was dried at 120 ° C and crushed coarsely, the crushed sediment was ignited (calcined) in the air at 600 ° C, crushed, and then the powder was molded by pressure in a tablet format that has a diameter of 3 mm with the use of a compression molder, thus producing a compact tablet. The compact was ignited in air at 950 ° C, and a compact of Ni ₀₁ M ₀₁ Mg ₀ 8O catalyst was prepared.
[00412] The catalyst was fixed using a silica wool in order to be located in the center of a SUS reaction tube, a thermocouple was inserted in the central position of the catalyst layer, and the fixed bed reaction tube was established in a predetermined location.
[00413] Before the start of a reform reaction, the temperature of the reaction container was increased to 800 ° C in a nitrogen atmosphere, and a reduction treatment was carried out for 30 minutes at the same time as hydrogen gas was being made. flow at 100 ml / min. After that, coke oven stimulating gas (crude gas) (hydrogen: nitrogen = 1: 1, 2,000 ppm H ₂ S was contained, and the total flow rate was 125 ml / min) was prepared and introduced into the reaction container. In addition, as a tar-stimulating substance generated during carbonization of coal, 1-methyl naphthalene which was a liquid substance that was actually contained in tar and had a low viscosity at room temperature was introduced into the reaction container as a typical substance in a flow rate of 0.025 g / min and was reacted at normal pressure.
[00414] As a result of collecting and observing the catalyst after the end of the test, a large amount of bulky shaped carbon was accumulated between the catalyst particles. As a result of sieving the catalyst particles and the accumulated substance, most of the bulky carbon in the su
117/137 catalyst surface was separated from the catalyst surface due to vibration several times, passed through the openings in the sieve, and released.
[00415] Therefore, it was observed that, in a case where the present catalyst was used, most of the solid carbon accumulated between the catalyst particles passed through the catalyst particles due to the slight agitation of the catalyst particles, and fell . Based on the result described above, it can be considered that when the apparatus of Test Example 1-1 or 1-3 is used in a reforming reaction in which the present catalyst is used, it is possible to significantly avoid fixing the product to the retention section in the catalyst layer and I block it in the catalyst layer.
TEST EXAMPLE 2-1
Configuration of the entire reaction system [00416] Carbonized carbon gas (containing water vapor derived from moisture in the coal) was continuously generated as raw material gas by supplying the coal to a calcination furnace heated from a supplier of coal (constant quantity supplier of coal hopper) at a rate of 20 kg / hour.
[00417] An inflow opening in a continuous fixed bed catalytic reactor that has a structure as illustrated in FIGS. 8A, 8B, 8C and 8D was connected to the calcination furnace using a heat retention tube, and an efflux opening in the continuous fixed bed catalytic reactor was connected to an induced draft fan using a scrubber using a heat retention tube.
[00418] The tar in the carbonized coal gas was reformed in the catalytic reaction container in order to generate light gas (hydrogen or similar), and the light gas was diffused into the atmosphere through a torch chimney (which subjects the gas to combustion) with the use of the induced draft fan.
118/137 [00419] The catalytic reaction container was accommodated in an electric heating oven that has a controlled oven temperature at a constant temperature. The flow rate of the induced draft fan could be adjusted and was controlled at a flow rate that corresponds to the carbonized gas per coal generation rate.
Catalyst [00420] 1) Material: a component system that forms
Ni0,1Ce0,1Mg0,8O [00421] Nickel nitrate, cerium nitrate and magnesium nitrate were weighed so that the molar ratio of the metal elements became 1: 1: 8, nickel, magnesium and cerium were co-precipitated as hydroxides adding an aqueous solution of potassium carbonate heated to 60 ° C to a mixed aqueous solution prepared at a heating temperature of 60 ° C, and were sufficiently stirred using a stirrer. After that, nickel, magnesium and cerium were aged by continuing to stir for a certain period of time while retaining nickel, magnesium and cerium were at 60 ° C, so they were filtered with suction, and were sufficiently washed with use of pure water (80 ° C). After the sedimentation obtained after washing was dried at 120 ° C and crushed coarsely, the crushed sediment was ignited (calcined) in the air at 600 ° C, crushed and then fed to a beaker. A sol alumina was added, the mixture was sufficiently mixed using a mixer equipped with a stirring blade and moved to an eggplant shaped jar. The eggplant-shaped flask was mounted on a rotary evaporator, and the mixture was sucked under stirring, thereby evaporating moisture. Nickel, magnesium, cerium and alumina compounds fixed to the wall surface of the jar in the shape of an eggplant were moved to a plate of
119/137 evaporation, dried at 120 ° C and calcined at 600 ° C. The powder was molded by pressure using a compression molder, thus producing a compact.
[00422] The compact was ignited in air at 950 ° C, and a catalyst compact was prepared by mixing 50% by weight of alumina with Ni ₀₁ Ce ₀₁ Mg ₀ 8O. As a result of confirming the components of the compact through ICP analysis, it was confirmed that the compact had the desired components. In addition, as a result of measuring the compact using a kyia type hardness meter, it was observed that the compact retains a high strength of approximately 100 N.
[00423] 2) The shape and dimensions of the catalyst particles:
cylindrical catalyst particles that have an outer diameter of 15 mm, an inner diameter of 5 mm, and a height of 15 mm.
[00424] 3) Quantity of catalyst used: 7 kg
Continuous fixed bed catalytic reactor [00425] A test was performed using a continuous fixed bed catalytic reactor that has the structure illustrated in FIGS. 8A, 8B, 8C and 8D. The continuous fixed bed catalytic reactor illustrated in FIGS. 8A, 8B, 8C and 8D has been arranged inside the electric heating oven so that it has the ability to be heated during a reaction.
[00426] Reaction container dimensions: 40 mm thick * 450 mm wide * 700 mm high [00427] Inlet opening was made to vent gas from a rectangular opening that has a height of 50 mm and a width 400 mm for the inflow and outflow tube of JIS80A [00428] Material: stainless steel [00429] Pin: a round stainless steel rod that has a diameter of 5.1 mm and a length of 90 mm. The top section was flat and the corner section was 1 mm face. All pins were
120/137 welded to the catalyst retainer substrate in the shape of an isosceles triangle that has a bottom side of 16 mm (in the width direction) and a height of 13.5 mm (on the thickness side).
[00430] Orifice ratio: 92%
Operating conditions [00431] Calcining furnace temperature: 750 ° C [00432] Electric heating furnace temperature: 800 ° C [00433] Flow rate of carbonized gas by coal: 10 Nm ³ / h at an average [00434 ] Ventilation period of carbonized gas by coal: five hours [00435] The catalyst described above was accommodated in the continuous fixed bed catalytic reactor illustrated in FIGS. 8A, 8B, 8C and 8D, and a thermocouple was inserted in the central position of the catalyst layer.
[00436] Before the start of a reform reaction, the reactor temperature was increased to 800 ° C in a nitrogen atmosphere, and a reduction treatment was carried out for 30 minutes at the same time as hydrogen gas was flowing to 80 NI / min. After that, the coke oven gas was adjusted and introduced, and the reaction was evaluated at normal pressure.
Results [00437] After the end of the test, while 20 g of solid carbon was accumulated on the substrate of the catalyst retainer, on the surface of the catalyst retainer, only a thin film of solid carbon was generated, there was no solid carbon fixation of shape bulky to the pins, and the ventilation resistance of the catalyst retainer was the same as the ventilation resistance when the retainer was installed.
[00438] Furthermore, as a result of investigating the properties of the accumulated solid carbon, it was observed that most
121/137 of the solid carbon was amorphous.
TEST EXAMPLE 2-2 [00439] A test was performed under the same conditions as in Test Example 2-1 except that the catalyst was retained by providing punch metal that has a bore diameter of 6 mm, a plate thickness of 0.8 mm and a 20% orifice ratio in the inflow opening instead of the catalyst retainer in Test Example 2-1.
Results [00440] Since the pressure loss in the catalytic reaction container exceeded the limit limit value (6 kPa) after three hours of ventilation of the carbonized gas by coal, the test was interrupted.
[00441] As a result of investigating the catalytic reaction container after cooling the device and opening the inflow and efflux opening after the test, all holes in the puncture metal were blocked with solid carbon.
[00442] In this state, 50 Pa (gauge pressure) of nitrogen (gas that did not cause a catalytic reaction) was supplied and the gas flow rate at the efflux opening was measured. Then, the solid carbon in the holes in the puncture metal is removed using a wire brush, and then the gas flow rate in the outflow opening was measured under the same conditions. As a result, the gas flow rate at the outflow opening after removing the solid carbon doubled the gas flow rate before removing the solid carbon. Therefore, it was observed that, in the catalyst retention method of the related technique, the precipitation of solid carbon in the retention section had a significant adverse effect on the ventilation property; however, according to Test Example 2-1, the catalyst retainer has rarely had an adverse effect on the ventilation property.
122/137
TEST EXAMPLE 2-3 [00443] A test was performed using a continuous fixed bed catalytic reactor that has the structure illustrated in FIG. 12.
[00444] Reaction container dimensions: 80 mm thick * 220 mm wide * 500 mm high [00445] Inlet opening: the top end of the reaction container was open to the JIS 80A efflux tube, and the bottom end was open to the inflow tube of JIS150A respectively. The pin retaining plate was retained at the central height of the inflow tube, and the portion exposed on the outer circumference of the pin for the inflow tube corresponded to the inflow opening.
[00446] The storage space for the solid carbon corresponded to the inflow tube region below the pin retaining plate.
[00447] The other conditions were the same as in Test Example 2-1, under which the test was performed.
Results [00448] There was no bulky solid carbon on the surfaces of the pins after the test. 10 g of solid carbon was accumulated on the pin retaining plate, and 10 g of solid carbon was accumulated in the storage space. Therefore, it was observed that it was possible to suppress an increase in resistance to ventilation caused by the pins buried by the solid carbon accumulated in the pin retaining plate.
REFERENCE EXAMPLE 2-1 [00449] Nickel nitrate, cerium nitrate, zirconium nitrate oxide and magnesium nitrate were weighed so that the molar ratio of the metal elements became 1: 1: 1: 7, nickel, cerium, zirconium and magnesium were co-precipitated as hydroxides by adding an aqueous solution of potassium carbonate heated to 60 ° C to a solution
123/137 mixed aqueous solution prepared at a heating temperature of 60 ° C and sufficiently stirred using a stirrer.
[00450] After that, nickel, cerium, zirconium and magnesium were aged, continuing to stir for a certain period of time while retaining nickel, cerium, zirconium and magnesium were at 60 ° C, so they were filtered by suction, and were sufficiently washed with pure water (80 ° C). After the sedimentation obtained after washing was dried at 120 ° C and coarsely crushed, the crushed element was calcined in the air at 600 ° C, crushed and then fed to a beaker. A sol alumina was added, the mixture was sufficiently mixed using a mixer equipped with a stirring blade and moved to an eggplant shaped jar. The eggplant-shaped flask was mounted on a rotary evaporator, and the mixture was sucked under stirring, thereby evaporating moisture. Nickel, magnesium and alumina compounds fixed to the wall surface of the flask in the shape of an eggplant were moved to an evaporation plate, dried at 120 ° C and calcined at 600 ° C. The powder was molded by pressure into a tablet format that has a diameter of 3 mm with the use of a compression molder, thus producing a compact tablet. The compact was ignited in air at 950 ° C, and a catalyst compact was prepared by mixing 50% by weight of alumina with Ni0.1Ce0.1Zr0.1Mg0.7O.
[00451] As a result of confirming the components of the compact through ICP analysis, it was confirmed that the compact had the desired components. In addition, as a result of an XRD measurement of the present prepared product, it was clarified that the prepared product was made from the phases of NiMgO, MgAl2O4 and CexZr _1-x O ₂ , and the size of the respective crystallites was 14 nm, 11 nm and
124/137 nm.
[00452] The catalyst was fixed using silica wool in order to be located in the center of a SUS reaction tube, a thermocouple was inserted in the central position of the catalyst layer, and the fixed bed reaction tube was established in a predetermined location.
[00453] Before the start of a reform reaction, first, the reactor temperature was increased to 800 ° C in a nitrogen atmosphere, and a reduction treatment was carried out for 30 minutes at the same time as gas was made. hydrogen flow at 100 ml / min. After that, coke oven stimulating gas (crude gas) (hydrogen: nitrogen = 1: 1, 2,000 ppm H ₂ S was contained, and the total flow rate was 125 ml / min) was prepared and introduced into the reaction container. In addition, as a tar-stimulating substance generated during carbonization of coal, 1-methyl naphthalene which was a liquid substance that was actually contained in tar and had a low viscosity at room temperature was introduced into the reaction container as a typical substance in a flow rate of 0.025 g / min, was reacted at normal pressure and was evaluated.
[00454] In the present reference example, a net was provided in the bottom section of the catalyst in the reaction tube, the catalyst was retained by fixing the net using silica wool in order to prevent the net from falling and, after At the end of the test, a large amount of solid carbon was attached to the entire network. Therefore, it was observed that, when the catalyst was used, part of the solid carbon was easily released and fixed to the network.
[00455] Furthermore, as a result of investigating the properties of a substance attached to the network after the test, it was observed that the substance was almost the same as the substance released from the catalyst in Test Example 2-1. Therefore, it can be considered that,
125/137 when the apparatus of Test Example 2-1 is used in a reform reaction in which the present catalyst is used, it is possible to significantly avoid fixing the product to the retention section in the catalyst layer and blocking in the catalyst.
REFERENCE EXAMPLE 2-2 [00456] Nickel, magnesium and sodium were weighed so that their atomic weights (%) became 10%, 80% and 10% respectively, nickel, magnesium and sodium were co-precipitated as hydroxides adding an aqueous solution of potassium carbonate heated to 60 ° C to a mixed aqueous solution prepared at a heating temperature of 60 ° C, and were sufficiently stirred using a stirrer. After that, nickel, magnesium and sodium were aged by continuing to stir for a period of time while retaining nickel, magnesium and sodium were at 60 ° C, so they were filtered by suction, and were sufficiently washed with pure water (80 ° C).
[00457] After the sedimentation obtained after washing was dried at 120 ° C and crushed coarsely, the crushed sediment was ignited (calcined) in the air at 600 ° C, crushed and then the powder was pressure molded into a tablet that has a diameter of 3 mm with the use of a compression molder, thus producing a compact tablet. The compact was ignited in air at 950 ° C, and a compact Ni ₀₁ M ₀₁ Mg ₀₈ O catalyst was prepared [00458] The catalyst was fixed using a silica wool in order to be located in the center of a SUS reaction, a thermocouple was inserted in the central position of the catalyst layer, and the fixed bed reaction tube was established in a predetermined location.
[00459] Before the start of a reform reaction, the reactor temperature was increased to 800 ° C in a nitrogen atmosphere, and
126/137 a reduction treatment was performed for 30 minutes at the same time as hydrogen gas was made to flow at 100 ml / min. After that, coke oven stimulating gas (crude gas) (hydrogen: nitrogen = 1: 1,200 ppm H ₂ S was contained, and the total flow rate was 125 ml / min) was prepared and introduced into the reaction container. In addition, as a tar-stimulating substance generated during carbon carbonization, 1-methyl naphthalene which was a liquid substance that was actually contained in tar and had a low viscosity at room temperature was introduced into the reactor as a typical substance at a rate flow rate of 0.025 g / min, was reacted at normal pressure and was evaluated.
[00460] In the present reference example, a net was provided in the bottom section of the catalyst in the reaction tube, the catalyst was retained by fixing the net using silica wool in order to prevent the net from falling and, after At the end of the test, a large amount of solid carbon was attached to the entire network. Therefore, it was observed that, when the catalyst was used, part of the solid carbon was easily released and fixed to the network. In addition, as a result of investigating the properties of a substance attached to the network after the test, it was observed that the substance was almost the same as the substance released from the catalyst in Test Example 2-1. Therefore, it can be considered that when the apparatus of Test Example 2-1 is used, it is possible to significantly avoid fixing the product to the retention section in the catalyst layer and blocking in the catalyst layer in a reform reaction in that the present catalyst is used.
TEST EXAMPLE 3-1
Configuration of the entire reaction system [00461] Gas carbonized by coal (which contains water vapor derived from moisture in the coal) was continuously generated by supplying coal to a calcination furnace heated from a gas supply
127/137 coal (constant quantity supplier of coal hopper) at a rate of 20 kg / hour. An inflow opening in a continuous fixed bed catalytic reactor was connected to the calcination furnace using a heat retention tube, and an outflow opening in the continuous fixed bed catalytic reactor was connected to an induced draft fan via a scrubber using a heat retention tube. The tar in the carbonized gas by coal was reformed in the catalytic reaction container in order to generate light gas (hydrogen or similar), and the light gas was diffused as the reformed gas in the atmosphere through a torch chimney (which subjects the reformed gas) with the use of the induced draft fan. The catalytic reaction container was accommodated in an electric heating oven that has a controlled oven temperature at a constant temperature. The flow rate of the induced draft fan could be adjusted and was controlled at a flow rate that corresponds to the carbonized gas per coal generation rate.
Continuous fixed bed catalytic reactor [00462] A test was performed using a continuous fixed bed catalytic reactor illustrated in FIGS. 15A, 15B and 15C. The reaction container was made of stainless steel, was 80 mm thick * 300 mm wide * 700 mm high and had a duct shape that had openings at the top and bottom. The top end of the duct in the reaction container was connected to the effluent tube of JIS 80A, and the bottom end of the duct was connected to the inflow tube of JIS150A, thereby venting the gas.
Operating conditions [00463] The operating conditions were as described below. [00464] Temperature of the charred furnace with charcoal: 750 ° C [00465] Temperature of the electric heating furnace: 800 ° C
128/137 [00466] Flow rate of carbonized gas by coal: 10 Nm ³ / h on an average [00467] Ventilation period of carbonized gas by coal: five hours [00468] Before the start of a reform reaction, first , the reactor temperature was increased to 800 ° C in a nitrogen atmosphere, and a reduction treatment was carried out for 30 minutes at the same time as hydrogen gas was flowing at 80 NI / min. After that, the coke oven gas was adjusted and introduced, and the reaction was evaluated at normal pressure.
[00469] 7 kg of the following catalyst was accommodated in the continuous fixed bed catalytic reactor illustrated in FIGS. 15A, 15B and 15C, and a thermocouple was inserted in the central position of the catalyst layer. (Catalyst) [00470] A catalyst that has a Ni ₀₁ Ce ₀₁ Mg ₀₈ O component system was used as the catalyst.
[00471] Nickel nitrate, cerium nitrate and magnesium nitrate were formed so that the molar ratio of the respective metallic elements became 1: 1: 8, nickel, magnesium and cerium were co-precipitated as hydroxides by the addition of an aqueous solution of potassium carbonate heated to 60 ° C for a mixed aqueous solution prepared at a heating temperature of 60 ° C and were stirred enough by the use of a stirrer. After that, nickel, magnesium and cerium were aged by continuing to stir for a certain period of time while the retention of nickel, magnesium and cerium was at 60 ° C, then they were suction filtered and washed enough using water pure (80 ° C). After the sediment obtained after washing was dried at 120 ° C and coarsely ground, the crushed sediment was incinerated (calcined) in air at 600 ° C, ground and then fed into a beaker. An alumina solution was added
129/137 nothing, the mixture was mixed enough by using a mixer equipped with a stirring blade and moved in an eggplant-shaped jar. The eggplant-shaped flask was mounted on a rotary evaporator and the mixture was aspirated under agitation, which thus evaporated the moisture. Nickel, magnesium, cerium and alumina compounds fixed to the surface of the eggplant-shaped flask wall were moved in an evaporation dish, dried at 120 ° C and calcined at 600 ° C. A powder was molded by pressure using a compression molder, which thus produces a compact cylindrical which has an external diameter of 15 mm, an internal diameter of 5 mm and a height of 15 mm.
[00472] The compact was fired in air at 950 ° C and a catalyst compact was prepared by mixing 50% by mass of alumina with Nio.iCeo.iMgo.8O. As a result of confirming the components of the compact through ICP analysis, it was confirmed that the compact had desired components. In addition, as a result of measuring the compact using a kiya-type hardness measurement, it was found that the compact retains a high strength of approximately 100 N.
Catalyst bar [00473] Round stainless steel rods having a diameter of 4 mm and a length of 500 mm were used as the central rods and cylindrical collars having a diameter of 10 mm were welded to a location 80 mm away from the end background, which prevents the catalyst particles from falling. The central rods in the catalyst particle series were welded to the bottom plate which was the retainer and 30 catalyst particles were manufactured to penetrate through the portion in the collars, which thus makes a catalyst bar. The series of catalyst particles was arranged in a zigzag shape in five lines in the direction of the thickness of the reaction vessel and in 14 or 15 lines in the direction of the width. Retaining plate drive mechanism [00474] Up and down stroke of the drive device: 20 mm [00475] Lifting speed of the drive device: 10 mm / second [00476] Lowering speed of the drive device: 80 mm / second [00477] Operating delay: the retaining plate has been moved reciprocally up and down three times in 3.5 hours after the carbonized carbon gas vent has started.
Results [00478] The results of the test will be described using FIG. 18. In FIG. 18, the horizontal axis represents the ventilation period, the left vertical axis represents the pressure loss in the reaction vessel and the right vertical axis represents the amplified hydrogen flow rate (the hydrogen flow rate generated in the container reaction by the reform reaction caused by the catalyst per unit mass of the catalyst). There was no particular increase in resistance to ventilation observed during the test. Although the performance of the reform slowly degraded after the initiation of carbonized carbon gas venting, the performance of the reform was suddenly recovered immediately after the reciprocal movement of the catalyst bar was performed.
[00479] As a result of cooling and disassembling the reaction vessel after the end of the test and investigation of the interior, while 50 g of solid carbon was accumulated in the bottom plate, there was no observable batch-shaped product attached to the catalyst particles.
TEST EXAMPLE 3-2
131/137 [00480] A test was performed using a continuous fixed bed catalytic reactor of FIGS. 16A, 16B and 16C. The test was performed in the same way as in Test Example 3-1 except for the fact that round stainless steel rods having a diameter of 4 mm and a length of 280 mm were used as the central rods, the series of particles of catalyst was welded to the retainer on one side at one end and was removably mounted on the retainer on the other side at the other ends, each catalyst particle series had 19 cylindrical catalyst particles penetrated, the catalyst particle series was arranged in one zigzag shape in five lines in the direction of thickness and in 22 lines in the direction of height on the catalyst bar, the catalyst bar was moved reciprocally in the vertical direction (the catalyst particles in the catalyst bar were moved in a direction of the diameter of the catalyst particle) and the catalyst bar was moved reciprocally in 8 hours 30 minutes and 9 hours 30 minutes after initialization to the ventilation.
Results [00481] The test results will be described using FIG. 21. In FIG. 21, the horizontal geometric axis represents the ventilation period and the vertical geometric axis represents the pressure loss in the reaction vessel. While the increase in the rate of resistance to ventilation was slightly greater than in Test Example 3-1 during the test, the pressure loss could be suddenly decreased immediately after performing the reciprocal movement of the catalyst bar twice.
[00482] The amount of carbon collected by cooling and disassembling the reaction vessel after the end of the test was 800 g.
[00483] There were no damaged catalyst particles observed.
132/137
REFERENCE EXAMPLE 3-1 [00484] Nickel nitrate, cerium nitrate, zirconium nitrate oxide and magnesium nitrate have been shaped so that the molar ratio of the respective metallic elements becomes 1: 1: 1: 7, nickel, cerium, zirconium and magnesium were co-precipitated as hydroxides by the addition of an aqueous solution of potassium carbonate heated to 60 ° C to a mixed aqueous solution prepared at a heating temperature of 60 ° C and was stirred enough by the use of a stirrer.
[00485] After that, nickel, cerium, zirconium and magnesium were aged by continuing to stir for a certain period of time while the retention of nickel, cerium, zirconium and magnesium was at 60 ° C, then they were filtered by suction and washed enough by using pure water (80 ° C). After the pellet obtained after washing was dried at 120 ° C and coarsely ground, the crushed pellet was calcined in the air at 600 ° C, ground and then fed into a beaker. An alumina solution was added, the mixture was mixed enough using a mixer equipped with the stirring blade and moved in an eggplant-shaped jar. The eggplant-shaped flask was mounted on a rotary evaporator and the mixture was aspirated under agitation, which thus evaporates moisture. Nickel, magnesium and alumina compounds fixed to the surface of the eggplant-shaped flask wall were moved in an evaporation dish, dried at 120 ° C and calcined at 600 ° C. The powder was molded by pressure into a tablet format that has a diameter of 3 mm by the use of a compression molder, which thus produces a compact tablet. The compact was set on fire in the air at 950 ° C and a catalyst compact was prepared by mixing 50% by weight of alumina with Ni ₀₁ Ce ₀₁ Zr ₀₁ Mg ₀₇ O.
[00486] As a result of the confirmation of the components of the com
133/137 pact through ICP analysis, it was confirmed that the compact had desired components. In addition, as a result of an XRD measurement of the present prepared product, it was clarified that the prepared product was manufactured from the NiMgO, MgAl2O4 and Ce _x Zr _1-x O2 phases and the size of the respective chrysolites was 14 nm, 11 nm and 22 nm.
[00487] The catalyst was fixed using silica wool in order to be located in the center of a SUS reaction tube, a thermoelement was inserted in the central position of the catalyst layer and the fixed bed reaction tube was defined in a predetermined location.
[00488] Before starting a reform reaction, first, the temperature of the reaction vessel was increased to up to 800 ° C in a nitrogen atmosphere and a reduction treatment was carried out for 30 minutes while making hydrogen gas flow at 100 ° C ml / min. After that, coke oven gas (raw gas) stimulating gas (hydrogen: nitrogen = 1: 1, 2,000 ppm H2S was contained and the total flow rate was 125 ml / min) was prepared and introduced into the reaction vessel . In addition, as a tar-stimulating substance generated during carbonization of coal, 1-methyl naphthalene which was a liquid substance that was actually contained in the tar and had a low viscosity at room temperature was introduced into the reaction vessel as a common substance at a flow rate of 0.025 g / min and was reacted at normal pressure.
[00489] As a result of collecting and observing the catalyst after the end of the test, a large amount of carbon in batch format was accumulated between the catalyst particles. As a result of sieving the catalyst particles and the accumulated substance, most of the batch-shaped carbon on the catalyst surface was separated from the catalyst due to several moments of fine vibration, passed through the sieve openings and fell.
[00490] Therefore, it was found that, in a case in which the presence
134/137 t and catalyst was used, most of the solid carbon accumulated between the catalyst particles passed through the catalyst particles due to the slight vibration of the catalyst particles and fell. Based on the result described above, it can be considered that when the apparatus of Test Example 3-1 or 3-2 is used in a reforming reaction in which the present catalyst is used, it is possible to significantly avoid the fixation of the solid product to the catalyst particles.
REFERENCE EXAMPLE 3-2 [00491] Nickel, magnesium and sodium were formed so that their atomic weights (%) became 10%, 80% and 10% respectively, nickel, magnesium and sodium were co-precipitated as hydroxides by the addition from an aqueous solution of potassium carbonate heated to 60 ° C to an aqueous solution mixed with that prepared at a heating temperature of 60 ° C and was stirred sufficiently by the use of a stirrer. After that, nickel, magnesium and sodium were aged by continuing to stir for a certain period of time while the retention of nickel, magnesium and sodium was at 60 ° C, then they were filtered by suction, and were washed enough by using water. pure (80 ° C).
[00492] After the pellet obtained after washing was dried at 120 ° C and coarsely ground, the crushed pellet was incinerated (calcined) in air at 600 ° C, ground and then powder was molded by pressure into a shape of tablet that has a diameter of 3 mm by the use of a compression molder, which thus produces a compact tablet. The compact was fired in air at 950 ° C and a compact of Ni ₀₁ M ₀₁ Mg ₀₈ O catalyst was prepared.
[00493] The catalyst was fixed using silica wool in order to be located in the center of a SUS reaction tube, a thermoelement was inserted in the central position of the catalyst layer and the
135/137 fixed bed reaction was defined at a predetermined location. [00494] Before starting a reform reaction, the temperature of the reaction vessel was increased to up to 800 ° C in a nitrogen atmosphere and a reduction treatment was carried out for 30 minutes while making hydrogen gas flow to 100 ml / min. After that, coke oven gas (raw gas) stimulating gas (hydrogen: nitrogen = 1: 1, 2,000 ppm H ₂ S were contained and the total flow rate was 125 ml / min) was prepared and introduced into the container reaction. In addition, as a tar-stimulating substance generated during carbonization of coal, 1-methyl naphthalene which was a liquid substance that was actually contained in the tar and had a low viscosity at room temperature was introduced into the reaction vessel as a common substance at a flow rate of 0.025 g / min and was reacted at normal pressure.
[00495] As a result of collecting and observing the catalyst after the end of the test, a large amount of carbon in a batch format was accumulated between the catalyst particles. As a result of sieving the catalyst particles and the product, most of the batch-shaped carbon on the catalyst surface was separated from the catalyst due to several moments of fine vibration, passed through the sieve openings and fell.
[00496] Therefore, it was found that, in a case in which the present catalyst was used, most of the solid carbon accumulated between the catalyst particles passed through the catalyst particles due to the slight vibration of the catalyst particles and fell. Based on the result described above, it can be considered that when the apparatus of Test Example 3-1 or 3-2 is used in a reforming reaction in which the present catalyst is used, it is possible to significantly avoid fixing the solid product to the catalyst particles.
136/137
INDUSTRIAL APPLICABILITY [00497] According to the invention, it is possible to provide a continuous fixed bed catalytic reactor that includes an effective unit to remove a solid product generated and accumulated in a large scale fixed bed catalyst layer and a reaction method catalytic in which crude gas material, particularly tar-containing crude gas material, is reformed highly effectively by the use of the continuous fixed bed catalytic reactor.
BRIEF DESCRIPTION OF THE REFERENCE SYMBOLS
CATALYTIC REACTION CONTAINER
CATALYST
PUNCHING METAL PLATE
RAW GAS MATERIAL
INFLUX OPENING
FLOW OPENING
REFORMED GAS
110 CONTINUOUS FIXED BED CATALYTIC BALLAST
111 REACTION CONTAINER
112, 112 'CATALYST SEAL
113 CATALYST LAYER
114 RAW GAS MATERIAL
115 REFORMED GAS
116 RAW GAS MATERIAL INFLUX TRAJECTORY
117 REFORMED GAS FLOW TRAJECTORY
118 ROD
119 FIXING TOOL
120 DRIVING MECHANISM
121 UP AND DOWN MOTION APPLIANCE
122 GEOMETRIC DRIVING AXLE
125 PIN
137/137
BACKGROUND PLATE
CATALYTIC REACTION CONTAINER
CATALYST LAYER
INFLUX TRAJECTORY
INFLUX OPENING
FLOW TRAJECTORY
FLOW OPENING
COVER
RAW GAS MATERIAL
REFORMED GAS
CATALYST RETAINER
ROUND TUBE
STORAGE SPACE
SKYLIGHT
FALLEN SUBSTANCE
CONTINUOUS FIXED BED BALL
REACTION CONTAINER
RETENTION PLATE
CATALYST PARTICLE SERIES
CATALYST BAR
DRIVING MECHANISM
UP AND DOWN MOTION APPLIANCE
GEOMETRIC DRIVING AXLE
RAW GAS MATERIAL
REFORMED GAS
RAW GAS MATERIAL INFLUX TRAJECTORY
REFORMED GAS FLOW TRAJECTORY
NECKLACE
CATALYST
CENTRAL STEM

权利要求:
Claims (16)
[1]
1. Continuous fixed bed catalytic reactor, characterized by the fact that it comprises:
an inflow path for crude gas material for a catalytic reaction and a flow path for reformed gas;
an immobile reaction container that is connected to the inflow path and the flow path, and retains a clustered catalyst, the clustered catalyst having external dimensions from 5 mm to 50 mm;
a catalyst retainer that has a venting property and retains the bundled catalyst, the catalyst retainer being provided in the immobile reaction container;
a space to store a liquid or solid foreign substance generated in a catalyst layer which is provided below the catalyst layer which is a collection of the clustered catalyst particles, and a drive mechanism that moves the clustered catalyst up and down by movement of the catalyst retainer up and down a state in which at least part of the catalyst particles that form the lateral outer circumferential surfaces of the catalyst layer are in contact with the inner wall of the immobile reaction container.
[2]
2. Continuous fixed bed catalytic reactor according to claim 1, characterized by the fact that a height of the catalyst layer is twice or less a thickness of the immobile reaction vessel, and is three times or more a maximum value of one common length of the external dimension of the grouped catalyst.
[3]
3. Continuous fixed bed catalytic reactor according to claim 1, characterized by the fact that
Petition 870190073921, of 08/01/2019, p. 12/19
2/5 the drive mechanism moves the grouped catalyst up and down so that an average speed of the grouped catalyst moving down is faster than an average speed of the grouped catalyst moving up.
[4]
4. Continuous fixed bed catalytic reactor according to claim 1, characterized by the fact that the catalyst retainer has a plurality of pins that are arranged in parallel with each other and that directly retain the catalyst grouped in a front end section.
[5]
5. Continuous fixed bed catalytic reactor according to claim 4, characterized by the fact that an inter-axis distance between adjacent pins in the plurality of pins satisfies a condition of [inter-axis distance between pins] [external pin diameter dimension] <[ minimum mesh size dimension that allows the grouped catalyst to traverse].
[6]
6. Continuous fixed bed catalytic reactor according to claim 4, characterized by the fact that a curvature in a contact section on the pin with the grouped catalyst is less than a maximum curvature on an external surface of the grouped catalyst.
[7]
7. Continuous fixed bed catalytic reactor according to claim 1, characterized in that the catalyst retainer includes central rods that form a series of catalyst particles by penetrating a plurality of the grouped catalyst particles, without impairing mobility of the grouped catalyst, and a retaining plate that supports the plurality of the central rods vertically.
[8]
8. Continuous fixed bed catalytic reactor according to claim 7, characterized by the fact that
Petition 870190073921, of 08/01/2019, p. 13/19
3/5 a material with a high thermal conductivity is used for the central rods, and a heating device is provided to heat end sections of the central rods.
[9]
9. Continuous fixed bed catalytic reactor according to claim 7, characterized by the fact that the drive mechanism moves the grouped catalyst up and down so that a speed of the central rod becomes slower than a speed of the particles of catalyst grouped in a terminal portion of reciprocal movement by the actuation mechanism.
[10]
10. Continuous fixed bed catalytic reactor according to any one of claims 1 to 9, characterized in that the continuous fixed bed catalytic reactor is also provided with a drive device for reciprocally moving the catalyst layer in the horizontal direction. .
[11]
11. Continuous fixed bed catalytic reaction method, characterized by the fact that a catalytic reaction is caused using the continuous fixed bed catalytic reactor, as defined in any one of claims 1 to 10, wherein the gas raw material is hydrocarbon-containing gas, and the products of a catalytic reaction are hydrocarbon in gas and solid or solid carbon.
[12]
12. Continuous fixed bed catalytic reaction method according to claim 11, characterized by the fact that the gas raw material is a tar containing gas.
[13]
13. Continuous fixed bed catalytic reaction method according to claim 12, characterized by the fact that the grouped catalyst is a complex oxide containing nickel, magnesium, cerium and aluminum and is manufactured from a complex oxide
Petition 870190073921, of 08/01/2019, p. 14/19
4/5 that does not contain alumina, in which the complex oxide can be manufactured from NiMgO, MgAbO4 and CeO2 crystal phases.
[14]
14. Continuous fixed bed catalytic reaction method according to claim 12, characterized by the fact that the grouped catalyst is made of a complex oxide containing nickel, magnesium, cerium, zirconium and aluminum, in which the complex oxide includes crystal phases of NiMgO, MgAl2O4 and CexZr1-xO2 (0 <x <1).
[15]
15. Continuous fixed bed catalytic reaction method according to claim 12, characterized by the fact that the grouped catalyst is a catalyst for reforming tar-containing gas which is a complex oxide represented by aM ^ bNLcMg ^ dO, in which a, b and c satisfy a + b + c = 1,
0.02 <to <0.98,
0.01 <b <0.97 and
0.01 <c <0.97, d represents a value at which oxygen and a positive element become electrically neutral,
M represents at least one element selected from Ti, Zr, Ca, W, Mn, Zn, Sr, Ba, Ta, Co, Mo, Re, platinum, rhenium, palladium, rhodium, Li, Na, K, Fe, Cu, Cr, La, Pr and Nd, at least one oxide selected from silica, alumina and zeolite is added to the complex oxide and an amount of the oxide selected from silica, alumina and zeolite is in a range of 1% by mass to 90% by mass in relation to complex oxide.
[16]
16. Continuous fixed bed catalytic reaction method according to any one of claims 11 to 15, characterized by the fact that
Petition 870190073921, of 08/01/2019, p. 15/19
5/5 the catalyst layer is moved both in the perpendicular and in the horizontal direction.

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KR101566650B1|2015-11-05|

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BR112014017557A2|2017-06-13|

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BR112014017557A8|2017-07-04|

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法律状态:
2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-06-04| B06T| Formal requirements before examination|

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2019-09-03| B25D| Requested change of name of applicant approved|Owner name: NIPPON STEEL CORPORATION (JP) |

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2019-12-24| B09A| Decision: intention to grant|

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2020-02-18| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/01/2013, OBSERVADAS AS CONDICOES LEGAIS. |

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