JP5272998B2 - Packing method in plate reactor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for uniformly charging a granular filler into the clearances between heat transfer plates of a plate type reactor. <P>SOLUTION: In the charging of the granular filler into the clearances between the heat transfer plates of the plate type reactor, when the repose angle of the filler is expressed by &theta;(&deg;C), the distance from a charging position of the filler in the axial direction of the heat transfer plate to the end of filling zone is expressed by B (m) and !0% (m) of the designed value of the height of the maximum point of a filler layer is expressed by E, the filler is charged from a charging position where B is equal to or below E/tan &theta;. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a method of filling a gap between heat transfer plates in a plate reactor with a packing material such as a particulate catalyst or inert particles.

  As a reactor for obtaining a reaction product by a gas phase catalytic reaction from a gaseous raw material in the presence of a particulate catalyst, a multitubular reactor or a plate reactor is known. Among these, as the plate reactor, for example, it has a reaction vessel for reacting gaseous raw materials, and a plurality of heat transfer plates provided side by side in the reaction vessel, the heat transfer plate, A plate-type reactor is known that includes a plurality of heat transfer tubes connected at the peripheral edge or edge of a cross-sectional shape, and is provided in the reaction vessel so that the heat transfer tubes are connected in the vertical direction (for example, Patent Documents). 1).

  In the multitubular reactor, the reaction tube is filled with a particulate catalyst. In a multi-tubular reactor, a catalyst is filled in a relatively thin tube, so that the catalyst is easily and sufficiently packed in the reaction tube regardless of its fluidity.

  On the other hand, in the plate reactor, a particulate catalyst is filled in a gap between adjacent heat transfer plates. In the plate reactor, since the catalyst is filled in the gap between the heat transfer plates, the catalyst flows in the axial direction of the heat transfer tube during filling. For this reason, when the catalyst is introduced from a plurality of positions in the axial direction of the heat transfer tube in the gap between the heat transfer plates, the catalyst is not uniformly filled in the gap between the heat transfer plates depending on the interval between the input positions. Variation in the position of the top surface of the packed bed in the gap may become large. It is feared that such a variation affects the control of the reaction when the plate reactor is used for the gas phase catalytic reaction.

JP 2004-202430 A

  The present invention provides a method that can uniformly fill the gaps between the heat transfer plates when the plate-type reactor is filled with the particulate packing.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies, paying attention to the relationship between the angle of repose of the particulate filler to be filled and the interval between the filling positions in the axial direction of the heat transfer tube. The invention has been completed.

  More specifically, the interval of the charging position of the packing material into the gap between the heat transfer plates of the plate reactor depends on the fluidity of the packing material to be packed. When the fluidity of the packing is defined by the angle of repose of the packing, the interval between the charging positions of the packing is related to the angle of repose of the packing to be filled.

For example, as shown in FIG. 1, when a filling material having a small angle of repose is introduced into the gap between the heat transfer plates at an appropriate interval, the filling material is uniformly filled. In addition, as shown in FIG. 2, when a filling material having a large angle of repose is introduced into the gap between the heat transfer plates at a relatively narrow interval, the filling material is also uniformly filled. On the other hand, even if the angle of repose is small, if the interval between the charging positions of the packing is too wide, the packing is filled unevenly as shown in FIG. As shown in FIG. 4, when the angle of repose of the filling is large, the filling is unevenly filled even if the interval between the filling positions is not so wide. In addition, the arrow in FIGS. 1-4 represents the injection | throwing-in position of the filling material to the said clearance gap.

  Therefore, in the present invention, in the filling of the packing into the gap between the heat transfer plates of the plate reactor, based on the flowability of the packing specified by the angle of repose, the packing is charged into the gap and flows. The filler is put into the gap from a specific position where a sufficiently uniform packed layer is formed.

That is, the present invention has a reaction vessel for reacting raw materials and a plurality of heat transfer plates provided side by side in the reaction vessel, and the heat transfer plates are connected by a peripheral edge or an edge of a cross-sectional shape. A plurality of heat transfer tubes that are provided in the reaction vessel so that the heat transfer tubes are connected in a vertical direction, and a particulate filler is introduced into a gap between adjacent heat transfer plates, and a packed bed is formed in the gap. Forming a packing in a plate-type reactor, a section where a packed bed is formed in the gap when the packing is filled into the gap from a single charging position, The repose angle of the packing is θ (°), the distance from the charging position to the end of the packing section in the axial direction of the heat transfer tube is B (m), and the height of the highest point of the packed bed is When 10% of the set value is E (m) In addition, the present invention provides a packing method in a plate reactor in which the packing is introduced into the gap so as to satisfy the following formula (1).
B ≦ E / tan θ (1)

Further, the present invention is a method of filling the filling material into a single filling section from a plurality of positions in the axial direction of the heat transfer tube, wherein the distance between adjacent charging positions is A (m). Furthermore, the filling method is provided in which the filler is introduced into the gap so as to satisfy the following formula (2).
A ≦ 2 × E / tan θ (2)

  In the present invention, the plate reactor further includes a partition that is disposed in the gap along the vertical direction and divides the gap in the vertical direction, and the filling section is a section formed by the partition. A filling method is provided.

  Moreover, this invention provides the said filling method whose length of the said filling division in the axial direction of the said heat exchanger tube is 0.05m-2m.

  In addition, the present invention provides the filling method, wherein the packing is one or both of a particulate catalyst and inert particles.

The present invention also includes a plurality of heat transfer plates provided side by side in a reaction vessel for reacting raw materials, and the heat transfer plates are connected in the vertical direction at the periphery or edge of the cross-sectional shape. A method for producing a reaction product from a raw material by a catalytic reaction using a plate reactor including a heat pipe, wherein the raw material is formed on a catalyst layer formed by dropping the catalyst into a gap between adjacent heat transfer plates At least one selected from the group consisting of ethylene, hydrocarbons having 3 and 4 carbon atoms, and tertiary butanol, and a step of supplying a heat medium having a desired temperature to the heat transfer tube. Or at least one selected from the group consisting of unsaturated aliphatic aldehydes having 3 and 4 carbon atoms; aliphatic hydrocarbons having 4 or more carbon atoms; o-xylene; olefins; Cumene hydroperoxide; butene; or ethylbenzene; and the reaction product obtained is ethylene oxide; at least one of unsaturated aliphatic aldehydes having 3 and 4 carbon atoms and unsaturated fatty acids having 3 and 4 carbon atoms Maleic acid; phthalic acid; paraffin; alcohol; acetone and phenol; butadiene; or styrene; wherein the plate reactor is provided with a method for producing a product using the packing method of the present invention.

  Further, the present invention provides the reaction product, wherein the raw material is propylene or isobutylene, and one or both of (meth) acrolein and (meth) acrylic acid is produced by oxidizing propylene or isobutylene using a molecular oxygen-containing gas. A manufacturing method is provided.

  In the present invention, since the packing is introduced into the gap so as to satisfy the formula (1), the packing is uniformly distributed in the gap between the heat transfer plates when filling the plate reactor. Can be filled.

  Further, according to the present invention, when the filling material is filled into one filling section from a plurality of positions in the axial direction of the heat transfer tube, the filling material is poured into the gap so as to further satisfy the formula (2). Therefore, even when the packing is filled in the plate reactor in which the packing is filled from a plurality of charging positions in one filling section, the packing can be uniformly filled in the gaps between the heat transfer plates.

  In the present invention, the plate reactor further includes a partition that is disposed in the gap along the vertical direction and divides the gap in the vertical direction, and the filling section is a section formed by the partition. However, it is more effective from the viewpoint of filling the gap between the heat transfer plates uniformly and easily.

  In the present invention, the length of the filling section in the axial direction of the heat transfer tube is 0.05 m to 2 m, which is more effective from the viewpoint of filling the gap between the heat transfer plates uniformly and easily. It is.

  Moreover, in this invention, it is more effective from the viewpoint of performing the gas phase contact reaction by a uniform packed bed that the said packing is one or both of a particulate catalyst and an inert particle.

It is the schematic when an example of the packed bed by which a packing is filled with the suitable space | interval in the clearance gap between the heat exchanger plates in a plate type reactor is seen from the heat exchanger plate side. It is the schematic when the other example of the packed bed by which a packing is filled with the suitable space | interval in the clearance gap between the heat exchanger plates in a plate type reactor is seen from the heat exchanger plate side. It is the schematic when an example of the packed bed by which a packing is filled with the gap | interval in the space | interval between heat-transfer plates in a plate-type reactor at an unsuitable space | interval is seen from the heat-transfer plate side. It is the schematic when the other example of the packed bed by which a packing is filled with the gap | interval in the space | interval between heat exchanger plates in a plate type reactor at an unsuitable space | interval is seen from the heat exchanger plate side. It is a figure which shows roughly the principal part of an example of the plate type reactor of this invention. It is a figure explaining the space | interval of the heat exchanger plate and the pipe diameter of a heat exchanger tube in the plate type reactor of FIG. It is a figure which shows schematically the structure in one Embodiment of the plate-type reactor of this invention. It is a figure which shows a cross section when the plate type reactor of FIG. 7 is cut | disconnected along A-A 'line. It is a figure which shows a cross section when the plate type reactor of FIG. 7 is cut | disconnected along B-B 'line. It is a figure which shows schematically the structure of the heat medium mixing apparatus in the plate type reactor of FIG. It is a figure which shows the partition 7 in the plate type reactor of FIG. It is a perspective view of the vent plug 8 in the plate type reactor of FIG. It is a figure which shows the latching state of the vent plug 8 to the partition 7. FIG. It is a figure which shows roughly an example of the instrument for filling used for this invention. It is a figure which shows schematically the other example of the filling instrument used for this invention. It is a figure which shows roughly an example of the apparatus for filling used for this invention. It is a figure which shows roughly an example of the apparatus for filling used for this invention. It is a figure which shows roughly the top part of the packed bed formed by the filling material being thrown into the clearance gap between heat-transfer plates from several injection | throwing-in positions. It is a figure which shows roughly an example of the distribution apparatus used for this invention.

The packing method of the packing material in the plate reactor according to the present invention is a packing space in which a packing layer is formed in the gap when the packing material is charged into the gap from one charging position. The repose angle of θ (°), the distance from the filling position in the axial direction of the heat transfer tube to the end of the filling section is B (m), and the height of the highest point of the packed bed is set to In this method, when 10% is E (m), the filler is put into the gap so as to satisfy the following formula (1).
B ≦ E / tan θ (1)

  The charging position is a side edge on the end side in the flow of the filling material charged into the gap. When the width of the flow of the packing is 0.05 m or less, the center of the flow of the packing may be used. If the width of the flow of the packing is narrow, the charging operation becomes easy, and if it is wide, the uniformity of the packed packing is easy to improve. The flow width of the packing is preferably 0.05 m or less from the viewpoint of workability of the charging operation. In addition, the width of the flow of the packing is preferably 0.1 m or more, and more preferably 0.15 m or more, from the viewpoint of improving the uniformity of the packed packing.

  The highest point of the packed bed is the highest position on the top surface when one filled section is filled with the filler. In the case where there is only one filling position per filling section, the highest height of the packed bed is the height of the filling layer at the filling position, and the filling position per filling section is In the case of a plurality, the height of the highest point of the packed bed is the maximum value of the height of the packed bed at the charging position. In the present invention, the set value of the height of the packed bed is set at the height of the highest point of the packed bed. For example, in the present invention, setting the height of the packed bed to 1.7 m means that the height of the highest point of the packed bed is set to 1.7 m. In the present invention, the filling of the packing is the difference between the set value of the highest point of the packed bed and the measured value of the highest point of the packed bed, which is the set value of the highest point of the packed bed. It is preferably performed so as to be 5% or less, and more preferably performed so as to be 3% or less.

  The E is 10% of the set value of the height of the highest point of the packed bed. The plate reactor in the present invention is preferably used for, for example, a gas phase catalytic reaction, and a particulate catalyst or a mixture of particles and inert particles is usually used as the packing. In the above-mentioned use and packing, the difference between the set value of the height of the highest point of the packed bed and the measured value of the packed bed height is equalization of the pressure during use by further uniform packing of the packing. And from a viewpoint of suppression of the fall of catalyst performance, it is preferable that it is a value of 5% or less of the said setting value, and it is more preferable that it is a value of 3% or less. When E is larger than 10%, the pressure of the catalyst layer at the time of the reaction becomes non-uniform in the above-mentioned use, the local reactant blows out, and the conversion rate of the reactant is lowered. The yield of can be reduced.

If B is larger than E / tan θ, the measured value of the height of the packed bed may be larger than E. The B may be equal to or less than E / tan θ, but a small B is preferable from the viewpoint of improving the uniformity of the filled material, but the number of the charging positions increases, and the charging operation of the packing material is complicated. May be. B is preferably 0.5 × E / tan θ or more, and more preferably 0.75 × E / tan θ or more, from the viewpoint of workability of the charging operation.

  The filling material can be charged into the filling section so as to obtain a packed bed having the set value. The charging of the filling material into such a filling section is obtained by obtaining the amount of filling material having the set value height at the charging position when the filling material is charged from the charging position in one filling section. It is possible to carry out by charging a filling amount of the filling material from the charging position. The input amount can be obtained from, for example, the volume of the filling section, the spatial density of the catalyst, the angle of repose of the catalyst, and the number of input positions in one filling section.

  Alternatively, the filling material can be charged into the filling section by charging the filling material from the charging position until the height of the highest point of the actual packed bed reaches the set value. The end point of charging of the filling material into such a filling section is marked on the heat transfer plate at the position where the set value is reached, and the camera is inserted into the gap visually from above the heat transfer plate. Fill the rod-shaped object by observing the height of the packed bed during filling, using a contact-type sensor that detects the position of the top surface of the packed bed that rises as the packing is charged, or from above It can be determined by measuring the position of the top surface in contact with the top surface of the layer.

  The quality of the formed packed bed can be evaluated by comparing the set value with the actually measured value or by comparing the filling height of the filling material in each filling section. For example, the formed packed layer may have an error of an actually measured value with respect to a set value of the height of the highest point of the packed layer within 0 to 10%, and more preferably within 0 to 5%.

  The method for putting the filler into the filling section is not particularly limited. As such a method, for example, charging of a filling material from a charging position by an operator and charging of a packing material from a charging position using a filling tool or apparatus can be cited. In some cases, the filling device or apparatus may be the same as or modified from the device or apparatus used to fill the reaction tube of the multi-tube reactor.

  It is preferable that the method of introducing the filling material into the filling compartment is a method capable of controlling the supply speed of the filling material into the filling compartment, and the supply amount of the filling material into the filling compartment is controlled. It is preferable that the method be able to. From these viewpoints, it is preferable to use a filling device having a container such as a hopper and a conveying device such as a belt conveyor that can freely adjust the speed, and the filling material is put into the filling section.

In the present invention, when filling the filling material into a single filling section from a plurality of charging positions, the filling material is placed in the gap so as to satisfy the following equation (2) in addition to the equation (1). throw into. Here, in the following formula (2), A is a distance (m) between the adjacent charging positions, and represents a distance between adjacent side edges in the flow of the adjacent packing.
A ≦ 2 × E / tan θ (2)

  If A is larger than 2 × E / tan θ, the measured value of the height of the packed bed may be larger than E. The A may be 2 × E / tan θ or less, but if A is small, like B, it is preferable from the viewpoint of improving the uniformity of the filled material, but the number of charging positions increases, The filling operation may be complicated. A is preferably 1 × E / tan θ or more, and more preferably 1.5 × E / tan θ or more, from the viewpoint of workability of the charging operation.

  In the present invention, when filling one filling section with a plurality of filling positions, the filling materials are simultaneously charged into one filling section. Here, simultaneous charging means that the same amount of filling material starts to be simultaneously charged at the same speed at each charging position. The charging amount and charging speed of the filling material at each charging position may be substantially the same. For example, the charging volume may be within ± 10% with respect to the average value of the charging volume at each charging position. May be within the range of + 10% of the loading time at the loading position at which the latest loading is completed with respect to the loading time at the loading position at which the loading is completed earliest.

  The filling section is a chamber that can accommodate the filling in a gap between the heat transfer plates. The filling section is the gap when a partition that partitions the gap in the vertical direction is not provided in the gap, and one section formed by the partition when the partition is provided in the gap. It is. The filling section can be adjusted in length in the axial direction of the heat transfer tube by providing the partition in the gap. When the length of the filling section in the axial direction of the heat transfer tube is short, it is easy to reduce the charging position of the packing material and to easily uniformly fill the packing material. As described above, the length of the filling section in the axial direction of the heat transfer tube is preferably 0.05 m to 2 m, and preferably 0.1 to 1 m from the viewpoint of workability of uniform filling of the packing. Is more preferable, and it is further more preferable that it is 0.2-0.5 m.

  The volume of the filling section by the heat transfer plate and the partition is preferably 1 to 100 L, and preferably 1.5 to 30 L, from the viewpoint of performing filling of the filling into the gap in units of sections and performing accurate and easy filling of the packing. More preferably, it is particularly preferably 2 to 15 L.

  As the filler, a particulate filler is used. One kind or two or more kinds of fillers may be used. In the case of two or more kinds, they can be mixed or stacked and filled. The packing is selected according to the application of the plate reactor. Examples of the packing include particulate catalysts and inert particles that are generally used in gas phase catalytic reactions. Examples of the catalyst include a Mo-Bi composite oxide catalyst and a Mo-V composite oxide catalyst as described in JP-A-2005-336142. Examples of the inert particles include particles made of a substance that is inert under the use conditions of the plate reactor, such as mullite, alumina, silicon carbide, silica, zirconia oxide, and titanium oxide.

  The shape and size of the filler are appropriately selected from a range that can be filled in the gaps of the heat transfer plates. Examples of the shape of the filler include a spherical shape, a columnar shape, a cylindrical shape, a star shape, a ring shape, a small piece shape, a net shape, and an indeterminate shape. For example, when the packing is a catalyst or an inert particle, the size of the packing is preferably 1 to 20 mm, more preferably 3 to 10 mm, and more preferably 4 to 8 mm. Is more preferable.

  The angle of repose is one of the indicators of the fluidity of the packing, and is represented by the angle of the surface of the packing that has flowed or just before flowing with respect to the horizontal plane. The smaller the angle of repose, the higher the fluidity of the filling, which is preferable from the viewpoint of uniformly filling the filling in the filling section. From such a point of view, the repose angle of the filler is preferably 60 ° or less, and more preferably 55 ° or less.

  The angle of repose of the packing can be adjusted by mixing particles having different fluidity. For example, when the filler is a particulate catalyst or inert particles, the fluidity of the filler can be increased by mixing inert particles such as mullite balls having excellent fluidity.

  The angle of repose of the packing is determined by, for example, rolling a cylindrical container containing a sufficient amount of packing at an appropriate speed and then stopping the rotation of the container so that the surface of the group of packings in the cylinder is flat relative to the horizontal plane. The angle formed can be measured by a so-called tilt method in which the angle of repose is obtained.

  The plate reactor filled with the packing by the packing method of the present invention can be used in a catalytic reaction in which a fluid raw material that passes through a packed bed containing a particulate catalyst is reacted in the presence of the catalyst. . Examples of the raw material include liquid and gas. Moreover, such a contact reaction can be performed based on a known technique relating to a catalyst and a raw material to be used and reaction conditions.

  The plate reactor according to the present invention can be suitably used particularly when the raw material is a gas that is difficult to remove heat compared to the case where the raw material is a liquid. Further, the present invention produces a product by a gas phase catalytic reaction with heat generation or a gas phase catalytic reaction with endotherm, which can be controlled by a heat medium flowing in a heat transfer tube in the presence of a particulate catalyst. It can be applied to the method.

  Examples of the gas phase catalytic reaction with exotherm include, for example, a gas phase that generates one or both of the unsaturated aldehyde and the corresponding unsaturated carboxylic acid from one or both of the unsaturated hydrocarbon and the corresponding unsaturated aldehyde. More specifically, for example, gas phase catalytic oxidation reaction that produces acrolein and acrylic acid or methacrolein and methacrylic acid from propylene or isobutylene, and acrylic acid or methacrylic acid from acrolein or methacrolein. Examples of the gas-phase catalytic oxidation reaction to be generated include.

  In addition, as the gas phase contact reaction in the contact reaction accompanied by heat generation, for example, at least one selected from the group consisting of hydrocarbons having 3 and 4 carbon atoms and tertiary butanol, or unsaturated compounds having 3 and 4 carbon atoms A reaction for producing at least one of an unsaturated aliphatic aldehyde having 3 and 4 carbon atoms and an unsaturated fatty acid having 3 and 4 carbon atoms from at least one selected from the group consisting of aliphatic aldehydes and oxygen. Reactions that produce maleic acid from aliphatic hydrocarbons with 4 or more carbon atoms and oxygen, reactions that produce phthalic acid from o-xylene and oxygen, reactions that produce paraffins by hydrogenation of olefins, butadiene by oxidative dehydrogenation of butene Reaction of producing ethylene oxide from ethylene and oxygen, and reaction of producing alcohol by hydrogenation of carbonyl compounds. Liquid phase contact reaction includes acetone and phenol by acid decomposition of cumene hydroperoxide. Reaction for producing.

  Examples of the gas phase contact reaction with endotherm include a reaction for producing styrene by dehydrogenation of ethylbenzene.

  The method for producing a reaction product in the present invention uses methacrolein, acrolein, methacrylic acid, acrylic resin by the gas phase catalytic reaction in the presence of a particulate catalyst using the plate reactor of the present invention in the above gas phase catalytic reaction. Acid, maleic acid, phthalic acid, styrene, n-butene, isobutene, n-butane, isobutane, butadiene or ethylene oxide are produced.

  In particular, it is a gas phase contact reaction, and it is very exothermic and heat removal is important, and the reaction yield decreases significantly due to the increase in differential pressure due to cracking and pulverization of the catalyst. It is preferable to use the plate reactor according to the present invention for the gas phase catalytic oxidation reaction for producing methacrylic acid and the gas phase catalytic oxidation reaction for producing acrylic acid or methacrylic acid from acrolein or methacrolein.

  The plate reactor has a reaction vessel for reacting a gaseous raw material, and a plurality of heat transfer plates provided side by side in the reaction vessel, and the heat transfer plate has a cross-sectional periphery. Or a plurality of heat transfer tubes connected at the edges, provided in the reaction vessel so that the heat transfer tubes are connected in the vertical direction, and a particulate filler is introduced into the gap between adjacent heat transfer plates Accordingly, a plate reactor in which a packed bed is formed in the gap can be used.

  The plate reactor has a structure shown in FIG. 5, for example. That is, the plate reactor has the heat transfer plates 1 arranged in opposition. The heat transfer plate 1 is arranged so that the axis of the heat transfer plate 1 is along the vertical direction, and the convex edge on the surface of one heat transfer plate 1 faces the concave edge on the surface of the other heat transfer plate 1. Is arranged. A catalyst layer 2 is formed by filling a gap between the heat transfer plates 1 with a catalyst or a mixture of a catalyst and inert particles. A raw material gas is supplied to the catalyst layer 2 from above to below. Therefore, the upper end of the gap between the opposed heat transfer plates 1 is the gas inlet 3, and the lower end of the gap is the gas outlet 4.

  The heat transfer plate 1 is formed in a shape in which a plurality of heat transfer tubes are connected at the periphery of the cross-sectional shape. Three types of heat transfer tubes 5-1 to 5-3 having different radii in the horizontal direction are used for the heat transfer tubes. In the axial direction of the heat transfer plate 1, the heat transfer tube 5-1 having the largest radius is disposed at the top of the heat transfer plate 1, and the heat transfer tube 5-2 having the second largest radius is disposed in the middle of the heat transfer plate 1. The heat transfer tube 5-3 that is disposed and has the smallest radius is disposed below the heat transfer plate 1.

  The catalyst layer 2 is sandwiched between the heat transfer tubes 5-1 and has the narrowest width. The first reaction zone where the supplied raw material gas reaches first and the heat transfer tubes 5-2 are sandwiched between the two layers. The second reaction zone where the gas that has passed through the first reaction zone reaches the second narrowest, and the third reaction zone that is sandwiched between the heat transfer tubes 5-3 and that has the widest width and that reaches the gas that has passed through the second reaction zone And are formed.

  In FIG. 5, the opposing heat transfer plates 1 have the same structure. As for the heat transfer plate 1, as shown in FIG. 6, P represents the distance between the axes of the heat transfer plate, and H is the diameter in the horizontal direction of the heat transfer tube (formed by laminating plates formed in a waveform. L represents the diameter in the vertical direction of the heat transfer tube (in the case of a heat transfer tube formed by laminating plates formed in a waveform, the waveform length).

  As the reaction vessel, a vessel in which a gaseous raw material (raw material gas) is supplied, a generated gas is discharged, and a plurality of heat transfer plates are accommodated side by side can be used. Since the plate reactor is generally used for the reaction in an atmosphere under a pressurized condition, the reaction vessel is from atmospheric pressure to 3 MPa (megapascal), preferably from atmospheric pressure to 1,000 kPa (kilopascal), more preferably A pressure-resistant container that can withstand an internal pressure from normal pressure to 300 kPa is preferable. As such a reaction container, for example, a shell formed of a cylinder or a part of a cylinder, a shell whose interior is divided by a plate member so as to accommodate a plurality of heat transfer plates, and a plurality of heat transfer plates Examples thereof include a container having a housing-like interior surrounded by a member constituting a flat inner surface so as to be accommodated.

  The number of heat transfer plates can be determined by the amount of catalyst used in the reaction, and is preferably 10 to 300 from the viewpoint of industrial production of the reaction product. Moreover, the space | interval of the opposing heat exchanger plate can be determined based on the magnitude | size of a packing, and the use of a plate type reactor. For example, when the plate reactor is used for a gas phase catalytic reaction, the distance between the heat transfer plates is determined by considering the general size of the particulate catalyst used for the gas phase catalytic reaction. Is preferably 10 to 50 mm, and more preferably 20 to 35 mm. Here, the axis of the heat transfer plate means this vertical line when all the heat transfer tubes are connected on one vertical line in the heat transfer plate, and the connection part of all the heat transfer tubes is not on one vertical line Refers to the vertical line through the midpoint in their horizontal direction.

The heat transfer plate includes a plurality of heat transfer tubes connected at a peripheral edge or an edge of a cross-sectional shape. Thus, the heat transfer plate is a plate-like body including a plurality of heat transfer tubes arranged in parallel. In the heat transfer plate, the heat transfer tubes may be directly connected or indirectly connected through an appropriate member such as a plate or a hinge. The heat transfer plate is formed by forming two steel plates by press forming or roll forming into a shape formed by directly or indirectly connecting the two divided shapes of the heat transfer tube, and joining the respective steel plates. Forming is preferable from the viewpoint of obtaining a heat transfer plate with high accuracy and low cost. The heat transfer plate may include only a single type of heat transfer tube, or may include a plurality of types of heat transfer tubes having different cross-sectional shapes.

  The heat transfer plate is provided in the reaction vessel so that the heat transfer tubes are connected in the vertical direction. In the heat transfer plate, the angle formed by the axis of the heat transfer tube and the vertical direction is 120 to 60 ° from the viewpoint of aligning the reaction state in the gaps between the heat transfer plates when used in the gas phase contact reaction. It is preferably 100 to 80 °, more preferably 90 °.

  Heat transfer between the gas flowing through the gap between the heat transfer plates and the heat transfer tube is promoted by the irregularities on the surface of the heat transfer plate caused by the heat transfer tubes causing disturbance of the gas flow. The angle is most preferably around 90 ° from the viewpoint of heat transfer. However, the pressure loss of the flowing gas is greatest when the angle is 90 °. When it is desired to keep the gas pressure loss low, the angle is preferably set to an angle other than 90 °. In this case, it is preferable to reverse the angle between the adjacent heat transfer plates from the viewpoint of equalizing the gas flow and the catalyst during filling.

  The length in the vertical direction of the heat transfer plate when provided in the reaction vessel (the direction in which the raw material passes) can be determined according to the use of the plate reactor, for example, when used for a gas phase catalytic reaction From the viewpoint of making the reaction product sufficiently long, it is generally preferably 0.5 to 10 m, more preferably 0.5 to 5 m, and even more preferably 0.5 to 3 m. . From the size of a normally available thin steel plate, two plates can be joined or combined when the length is 1.5 m or more.

  The width of the heat transfer plate (that is, the length of the heat transfer tube) can be determined based on the reaction conditions in the gas phase catalytic reaction. For example, the width of the heat transfer plate is preferably 0.5 to 20 m, more preferably 3 to 15 m, and more preferably 6 to 10 m from the viewpoint of controlling the reaction temperature by the heat medium flowing through the heat transfer tube. Is more preferable.

  The heat transfer plate is formed of a material having heat transfer properties. Examples of such materials include stainless steel and carbon steel, hastelloy, titanium, aluminum, engineering plastic, and copper. Stainless steel is preferably used. For stainless steel, 304, 304L, 316, and 316L are preferred.

  The plate thickness of the thin plate constituting the heat transfer plate is preferably 2 mm or less, and more preferably 1 mm or less.

  The heat transfer tube is a tube having a heat transfer property through which a heat medium can flow. The cross-sectional shape of the heat transfer tube is not particularly limited. Examples of the cross-sectional shape of the heat transfer tube include a circular shape, a substantially circular shape such as an elliptical shape and a rugby ball shape, a leaf shape formed by symmetrically connecting arcs, and a rectangular shape. An example is a square. The peripheral edge in the cross-sectional shape of the heat transfer tube means a peripheral edge in a circular shape, and the end edge in the cross-sectional shape of the heat transfer tube means an edge of a major axis end in a substantially circular shape or a single edge in a polygon.

  The tube diameter of the heat transfer tube can be determined from the viewpoint of contact between the heat transfer tube and the filler. The tube diameter of the heat transfer tube is preferably 5 to 100 mm, considering the general particle size of the particulate catalyst used in the gas phase contact reaction, for example, and the short diameter of the heat transfer tube Is preferably 5 to 50 mm, and more preferably 10 to 30 mm. The major axis of the heat transfer tube is preferably 10 to 100 mm, and more preferably 20 to 50 mm.

  As a plate type reactor using such a heat transfer plate, two corrugated plates shaped like arcs, elliptical arcs, rectangles or polygons face each other, and the convex portions of the corrugated plates are mutually connected. A plurality of heat transfer plates joined together to form a plurality of heat medium flow paths are arranged, and the corrugated convex surface portion and the corrugated concave surface portion of the adjacent heat transfer plates face each other to form a catalyst layer at a predetermined interval. The formed reactor can be suitably exemplified.

  The plate reactor of the present invention may further have other components other than the components described above. Such other components include, for example, a heat medium supply device for supplying a heat medium to the heat transfer tube, a partition that is arranged in the gap in the vertical direction and divides the gap in the vertical direction, and ventilation And a vent plug that detachably closes the end of the compartment.

  The heat medium supply device is a device for supplying a heat medium having a desired temperature to a heat transfer tube of a heat transfer plate accommodated in the reaction vessel. The heat medium supply device is preferable from the viewpoint of precisely controlling the gas phase contact reaction. As such a heat medium supply device, for example, a device having a circulation channel for circulating the heat medium between the heat transfer tube and the outside thereof, and a temperature adjusting device for adjusting the temperature of the heat medium in the circulation channel Is mentioned. Examples of the temperature adjusting device include a heat exchanger and a heat medium mixing device for mixing a heat medium having a different temperature with the heat medium in the circulation flow path.

  The partition is a member that is provided in the gap between the heat transfer plates along the vertical direction and prevents the leakage of the filling material from the partition formed by the partition. The partition is preferable from the viewpoint of uniformly and easily filling the gaps with the filler by uniformly filling the filler for each section. The partition can be used as a spacer that maintains the distance between the heat transfer plates if it has rigidity enough to maintain its shape when the filling is filled in the compartment. Examples of the partition include stainless steel, carbon steel, hastelloy, titanium, aluminum, engineering plastic and copper plates, square bars, round bars, nets; glass wool; and ceramic plates.

  The vent plug is a member for freely opening and closing an end portion in the vertical direction of the section for each section. The vent plug is preferable from the viewpoint of easily extracting the filling for each section. As the vent plug, for example, a vent plate that covers the end of the partition, and a vent plate that is provided on the vent plate, is detachably locked to a heat transfer plate or partition, and the latch is secured from above or below the partition. And a member having a locking member that can be released.

  As the plate reactor, for example, as shown in FIGS. 7 to 9, a plurality of heat transfer plates 1 having a rectangular casing 6 and a heat transfer tube 5 and arranged in parallel facing each other in the casing 6, A gap between the heat transfer device 1 for supplying the heat transfer tube 5 and the adjacent heat transfer plate 1 and the adjacent heat transfer plate 1 is divided into a plurality of compartments filled and held with the filler along the ventilation direction in the casing 6. A plate reactor having a plurality of partitions 7, a plurality of vent plugs 8 having air permeability and closing the lower end portions of the respective sections, and a perforated plate 9 provided on the upper portion of the heat transfer plate 1 can be mentioned.

  The casing 6 forms an air passage having a rectangular cross section, and corresponds to the reaction vessel. The casing 6 has a pair of opposed vents 10 and 10 ′ at the upper and lower ends of the casing 6. The casing end 11 including the vent 10 and the casing end 11 ′ including the vent 10 ′. And a casing body in which the heat transfer plate 1 is accommodated. The casing end portions 11 and 11 'are detachably connected to the casing body.

  The heat transfer plate 1 is the heat transfer plate described above. The heat transfer tube 5 is also the heat transfer tube described above, and is a tube having a leaf-like cross-sectional shape in which two arcs are symmetrically connected at both ends and a heat transfer property. As described above, three types of heat transfer tubes 5-1 to 5-3 are used for the heat transfer tubes 5.

  The heat medium supply device is provided on a pair of opposing walls of the casing 6. A supply port for supplying a heat medium to each heat transfer tube 5 is formed in this wall. For example, as shown in FIG. 7, the heating medium supply device includes a pair of jackets 12, a circulation channel 13 for circulating the heating medium inside and outside one jacket 12, a pump 14 provided in the circulation channel 13, and circulation. A heat exchanger 15 for adjusting the temperature of the heat medium in the flow path 13 and a heat medium mixing device for further mixing the heat medium with the heat medium in the jacket 4 are configured. For example, in the entire reaction vessel, the jacket 12 is divided into a plurality at a predetermined height so that the heat medium meanders between the jackets 12 via the heat transfer tubes 5.

  For example, as shown in FIG. 8, the heating medium mixing apparatus includes a nozzle 16 communicating with the inside and outside of the jacket 12, a nozzle 16 connected to the inside of the jacket 12, and a direction orthogonal to the flow direction of the heating medium within the jacket 12. And a distribution pipe 17 extending to the center. The distribution pipe 17 is a pipe having a closed end and provided with a plurality of holes over the entire length of the distribution pipe.

  As shown in FIG. 11, the partition 7 is a stainless steel plate having a side edge that is in close contact with the irregularities on the surface of the heat transfer plate 1, and has a horizontally long rectangular window 18 at the lower end. The partition 7 is provided along the vertical direction in the gap between the opposed heat transfer plates 1. The partitions 7 are provided at equal intervals so as to form a predetermined volume section in the gap.

  As shown in FIG. 12, the vent plug 8 includes a rectangular vent plate 19 having the same cross-sectional shape in each section, a first skirt portion 20 suspended downward from the short side of the vent plate 19, and the vent plate 19. And a second skirt portion 21 that hangs downward from the long side. The first skirt portion 20 is formed with a rectangular locking window 22 and a locking claw 23 provided adjacent thereto.

  The ventilation plate 19 is a plate in which, for example, circular holes of 2 mm are formed with an opening ratio of 30%. The locking window 22 is formed in a size having a width and a height for accommodating the locking claw 23. The locking claw 23 is formed by bending two parallel cuts from the lower end edge of the first skirt portion 20 so as to protrude outward. In the pair of first skirt portions 20 facing each other, one locking window 22 and the other locking claw 23 face each other, and one locking claw 23 and the other locking window 22 face each other. The window 18 of the partition 7 is formed in a size having a width and a height that include the locking window 22 and the locking claw 23 at the same time.

  The vent plug 8 is inserted into each section from the lower end of each section with the ventilation plate 19 up. When the vent plug 8 is inserted, the locking claw 23 is pressed against the partition 7 against the outward bias, but when it reaches the window 18, as shown in FIG. Is released and is advanced toward the window 18 and is locked to the window 18.

  The perforated plate 9 is, for example, a plate in which holes having a diameter of 0.3 to 0.8 times the longest diameter of the filled material are provided with an opening ratio of 20 to 40%. The perforated plate 9 is disposed on the outermost side as shown in FIG. 7 in order to prevent air from flowing into the gap between the outermost heat transfer plate 1 and the wall of the casing 6. It is formed so as to close the gap from the edge of the heat plate 1 to the wall of the casing 6.

  In this plate-type reactor, filling of the packing into the gaps between the heat transfer plates 1 is performed by filling each compartment from above the heat transfer plate 1. The filling is performed from the charging position, which is a desired position according to the distance from the end of the section in the vertical direction. In the filling of the packing, an amount of packing corresponding to the volume of the section and the number of positions where the packing is charged into the section is charged into the section.

  Examples of the packing include a Mo-Bi composite oxide catalyst, a Mo-V composite oxide catalyst for producing acrolein and acrylic acid by a gas phase catalytic oxidation reaction of hydrocarbons such as propane and propylene, and mullite. Inactive particles such as alumina, silicon carbide, silica, zirconia oxide, and titanium oxide are used. When a catalyst and inert particles are used, the catalyst and the inert substance are mixed or laminated. The content of the inert particles in the mixing or lamination is, for example, 1 to 400 parts by mass with respect to 100 parts by mass of the catalyst. For example, the catalyst has a spherical shape, a cylindrical shape, a ring shape, a star shape, and the like, and the inert particles have a spherical shape, a cylindrical shape, a ring shape, a star shape, and the like.

  In the axial direction (horizontal direction) of the heat transfer tube 5, the distance from the charging position of the packing to the end of the section is B (m), the repose angle of the packing is θ (°), and the packed bed formed in the section When 10% of the reference value of height (set value of the height of the highest point of the catalyst layer) is E (m), when the width of the section is 2B or less, that is, 2 × tan θ / E or less, the charging position Can be determined at any one location where the distance from each end of the partition in the horizontal direction is tan θ / E or less.

  Thus, when there is one input position with respect to one filling section, the filling material of the quantity according to the volume of the filling section can be filled for every filling section. For example, in the filling of such a filling material, the filling material can be filled from a container such as a beaker at an appropriate rate of 50 to 5,000 mL / min.

  Alternatively, for example, as shown in FIG. 14, the filling of the filling material is performed on a rectangular plate 31, a frame 32 erected from each of the three sides of the plate 31, and a frame 32 at the center of the three sides. This can be done using a filling instrument having a handle 33 provided. Examples of the material for the filling device include stainless steel.

  As shown in FIG. 15, the filling device has a height lower than the maximum particle size of the filling material for guiding the filling material from the central side toward the opposite side having no frame. The guide plate 34 may be further included. One guide plate 34 or two or more guide plates 34 may be used. The filling instrument having such a guide plate 34 is shown in FIG. 14 from the viewpoint of setting the width of the flow of the filler to be charged into the filling section as the width of the opening (side having no frame) of the instrument. More preferred than the filling device shown.

  When filling the filling material using these filling tools, after the filling material is placed on the plate 31, the holding material 33 is shaken to the left and right and the filling material is leveled and dispersed without overlapping vertically. Then, the filling material can be put into the filling section at an appropriate speed of 50 to 5,000 mL / min so that the filling material does not overlap vertically from the full width of the opening.

  Alternatively, for example, as shown in FIG. 16, the filling of the filling material includes a hopper 35 for containing the filling material, a rectangular conveyance surface 36 to which the filling material is supplied from the hopper 35, and the conveyance surface 36. A frame 37 provided so as to stand up from the three sides, a regulating member 38 for regulating the height of the filling material conveyed on the conveying surface 36 to a desired height, and a filling material on the conveying surface 36 It can carry out using the filling apparatus which has the conveying apparatus which conveys toward 36 opening parts (side which does not have a frame in the conveyance surface 36).

  As shown in FIG. 16, the transport device includes a belt conveyor 39 that forms a transport surface 36 and is driven from the central side of the three sides provided with the hopper 35 toward the opening. As shown in FIG. 17, there is a vibrator 40 that vibrates a plate constituting a smooth conveying surface 36 inclined from the hopper 35 toward the opening.

As shown in FIG. 16, the filling device may further include a partition plate 41 that partitions the transport surface 36 along the transport direction of the filler. Such a partition plate 41 is preferable from the viewpoint of leveling the filling material on the conveying surface 36 in the width direction of the opening.

  In the filling apparatus, the filling material conveyed toward the opening on the conveying surface 36 is regulated by the regulating member 38 and overlapped in the width direction of the opening when overlapping, and has the same width as the opening. Into the filling section through the opening. The filling apparatus shown in FIG. 16 is preferable from the viewpoint of preventing breakage such as cracking and pulverization of the filler due to conveyance because the filler is conveyed by a belt conveyor. Moreover, since the packing apparatus shown in FIG. 17 conveys a packing by a vibrator, the structure of the packing apparatus becomes simpler, and is preferable from the viewpoint of workability of packing the packing in the plate reactor.

  In addition, about the opening part in FIGS. 14-17, the width | variety of the flow of the filler thrown in from an opening part is a width | variety of an opening part normally. Thus, the width of the flow of the packing can be changed by the filling method and the adjustment of the width of the opening. When the packing flow width is 0.05 m or less, the center of the packing flow width in the axial direction of the heat transfer tube is the charging position, and the packing flow width exceeds 0.05 m. Among the side edges of the packing material flow in the axial direction of the heat transfer tube, the position of the end of the target packing section or the side edge of the adjacent packing material flow side is the charging position.

  When the width of the section is 2B or more, that is, 2 × tan θ / E or more, the loading position is tan θ / E or less from each end of the section in the horizontal direction, and the adjacent positions When the distance between the input positions is A (m), it can be determined as two or more arbitrary locations where A is 2 × E / tan θ or less.

  For example, as shown in FIG. 18, assuming that the interval between the input positions is A, the angle of repose of the packing is θ, and the height difference formed on the top surface of the formed packed bed is d, d is A / 2 × tan θ. It is represented by Here, if the set value of the height of the highest point of the packed bed is L and a height difference of 10% or less is allowed with respect to the height of the highest point of the packed bed, d is 0.1 × L or lower. is there. Therefore, A is 0.1 × L × 2 / tan θ or less. For example, when the setting value of the height of the highest point of the packed bed is 1.7 m, A is 0.41 m or less when θ is 40 °, and A is 0.29 m or less when θ is 50 °. The distance B between the input position closest to the end of the section and the end of the section is set to A / 2 or less.

  When there are two or more charging positions for one filling section, the filling material is filled simultaneously from each charging position. In such a filling, when the volume of the filling section is constant, the amount of the filling obtained by dividing the volume of the filling section by the number of charging positions can be simultaneously charged into the filling section from each charging position. Alternatively, the filling sections can be simultaneously charged from each charging position at an appropriate arbitrary speed of 50 to 5,000 mL / min.

  Such filling can be performed by using, for example, a dispensing apparatus shown in FIG. 19 in combination with the filling apparatus shown in FIGS. This distribution device includes a plurality of dividing plates 42 that equally divide the opening of the conveying surface 36 in the width direction, a plurality of funnels 43 to which the packing divided by the dividing plates 42 is supplied, and the divided packing. And a plurality of supply pipes 44 for supplying the water from each funnel 43 to a desired charging position of a desired filling section. The supply pipe 44 can be freely rotated in the horizontal direction by using the elbow 45, and the length can be freely set by using an expansion / contraction pipe or connecting an appropriate length pipe by a joint.

  According to such filling of the packing material, it is easy to obtain a uniform packing layer in which the height of the top surface of the packing layer is entirely included in the range of 90 to 100% of the measured value of the height of the highest point of the packing layer. Can be formed.

  Set the setting value of the packed bed to an arbitrary height other than the highest point in the packed bed, such as the lowest point of the packed bed or the midpoint between the lowest point and the highest point, and based on this different set value Even when the filling material is filled based on the above-described equations (1) and (2), the height of the top surface of the packed bed is the height of the highest point of the packed bed. It is possible to easily form a uniform packed layer that is entirely included in the range of 90 to 100% of the actually measured value.

  Further, according to the filling of the packing described above, when there are two or more charging positions with respect to one filling section, a packed bed in which the position of the top surface of the packing is within an allowable range is formed in each section. Thus, the filling can be filled uniformly. In addition, the said distribution apparatus can be used also for the injection | throwing-in of the filling material to several filling divisions in the case of one injection | pouring location with respect to one filling division.

  Further, since the plate type reactor has the partition 7, the volume of each section formed by the partition 7 is sufficiently smaller than the gap, so that the packing can be easily and evenly charged. This is more effective from the viewpoint of easily and evenly filling the entire gap with the filler.

  In addition, although the illustrated plate type reactor has the partition 7, in the plate type reactor which does not have the partition 7, the above-mentioned plate type reaction is made with one gap between the heat transfer plates 1 as one filling section. As with the filling of the vessel compartment, the filling can be charged into the filling compartment.

  The filler can be extracted for each section by removing the vent plug 8 from the gap. The vent plug 8 is removed by pushing the locking claw 23 from the lower end of the adjacent section to release the locking claw 23 from being locked to the window 18. Thus, the filling of the filling can be easily performed for each section, and is more effective from the viewpoint of filling the filling equally and easily.

  In a plate reactor filled with a packing material, for example, a raw material gas is supplied from above to below in the gap, and a heat medium is supplied to the heat transfer tube 5 to produce a reaction product. For example, by supplying a raw material gas composed of propylene, air, and water vapor from the vent 10 and supplying a heat medium of 300 to 350 ° C. from the heat medium supply device to the heat transfer tube 5, for example, from bottom to top, Acrolein and acrylic acid are generated, and the generated acrolein and acrylic acid are discharged from the vent 10 '. The internal pressure of the plate reactor during the reaction is, for example, 150 to 200 kPa (kilopascal). Heat generated by the oxidation is absorbed by the heat medium flowing in the heat transfer tube 5.

  In the production of acrolein and acrylic acid, the temperature of the heat medium is set to a predetermined temperature by passing the heat medium through the heat transfer tube 5 in sequence, by the heat exchanger 15 and further from the heat medium mixing device to the heat medium in the jacket 12. When the reaction raw material is propylene, the temperature of the heat medium supplied to the plurality of reaction zones is preferably 250 to 400 ° C, and preferably 320 to 400 ° C. Is more preferable. On the other hand, when the reaction raw material is acrolein, the temperature of the heat medium supplied to the plurality of reaction zones is preferably 200 to 350 ° C, and more preferably 250 to 320 ° C.

  In the plate reactor, a packed bed is formed in which the packing is uniformly filled in the gap, such as generation of pressure loss in the packed bed and partial aeration of the packed bed, etc. The phenomenon resulting from the density of the packing state in the catalyst layer 2 is suppressed, and the production of acrolein and acrylic acid can be stably performed for a long period of time with high efficiency.

[Production of plate reactor]
As the plate reactor, a reactor having the structure shown in FIG. 5 was used. About the heat transfer plate, it has a thickness so as to have three types of corrugations that form the first, second, and third reaction zones from the upstream side along the flow direction of the source gas when the heat transfer plate is arranged. A 1 mm stainless steel plate was formed, and two obtained corrugated stainless steel plates were joined to form a heat transfer plate in which a plurality of heat transfer tubes serving as heat medium flow paths for reaction temperature adjustment were connected. Table 1 shows the period length (L), height (H), and number of waves of the waveform shown in FIG. 6 in the heat transfer plate.

  As shown in FIGS. 5 and 6, the pair of heat transfer plates shown in Table 1 are parallel to each other so that the convex edge of one heat transfer plate faces the concave edge of the other heat transfer plate, and The reactors were manufactured with a spacing of 26 mm (P shown in FIG. 6). The width of the heat transfer plate (the length of the heat transfer tube) was 1,000 mm.

[Preparation of catalyst]
Mo ₁₂ Bi ₅ Co ₃ Ni ₂ Fe _0.4 Na _0.4 B _0.2 K _0.08 as a catalyst used for catalytic vapor phase oxidation with molecular oxygen and conversion to acrolein and acrylic acid A metal oxide powder having a composition of Si ₂₄ O _x was prepared. Here, _x of O _x is a number determined by the oxidation state of each metal oxide. The obtained powder was molded to obtain a cylindrical molded product having an outer diameter of 4 mm and a height of 3 mm. The obtained molded product was calcined at 510 ° C. for 4 hours in the presence of air to obtain a composite oxide catalyst A. The powder was molded to obtain a ring-shaped molded product having an outer diameter of 6 mm, an inner diameter of 2 mm, and a height of 6 mm. The obtained molded product was fired in the same manner to obtain Catalyst B. The angle of repose of the obtained catalyst was determined by the method shown below.

[Measurement of repose angle]
As the measuring device, a three-wheeled cylindrical rotating surface angle measuring device GFL-68 manufactured by Tsutsui Rika Machinery Co., Ltd. was used. 250 g of catalyst is placed in a 500 mL container and placed on a pedestal. The cylinder is rotated at 10 rpm for 60 seconds, then the number of rotations of the cylinder is decreased to 2 rpm and rotated for 10 seconds, the switch is turned off, and the axial direction of the cylinder is traversed. The angle formed by the catalyst surface in the cross section with respect to the horizontal direction was measured as the angle of repose. The angle of repose of catalyst A was 45 °. Further, the repose angle of the catalyst B was 52 °.

[Example 1]
Catalyst A was filled in the gap between the heat transfer plates in the plate reactor. Positions 0.17 m, 0.50 m, and 0.83 m along the axial direction of the heat transfer tube from the end of the heat transfer plate are set as input positions (that is, the distance from both ends of the heat transfer plate to the closest input position is 0.17 m) , Set the charging position so that the distance between other charging positions adjacent to each other is 0.33 m), and simultaneously beaker from each charging position so that the height of the highest point of the packed bed is 1.73 m Used to fill the gap with a total of 24.9 L of catalyst at 200 mL per minute. After filling, the height of the catalyst layer was measured at 0 m, 0.17 m, 0.335 m, 0.50 m, 0.665 m, 0.83 m, and 1 m from the end of the heat transfer plate.

  Of the measured catalyst layer height, the height of the catalyst layer at the measurement position of 0.5 m was 1.73 m, which was the highest. Using the height of the catalyst layer as a reference (maximum point), the difference in height of the catalyst layer at other measurement positions with respect to the height of the catalyst layer at the measurement position of 0.50 m was determined. The height of the catalyst layer was determined by measuring the position of the top surface by bringing a stainless steel rod into contact with the top surface of the packed bed from above. The results are shown in Table 2. At each measurement position, the difference in the height of the catalyst layer at the other measurement position with respect to the height of the catalyst layer at the measurement position of 0.50 m is 10 times the height of the catalyst layer of 1.73 m at the measurement position of 0.50 m. It was within the range of 0.173 m which is within%.

[Comparative Example 1]
The charging position is set to 0.25 m and 0.75 m from one end of the heat transfer plate (that is, the distance from both ends of the heat transfer plate to the closest charging position is 0.25 m, and other adjacent charging positions Except that the charging position was set to 0.50 m), a total of 24.1 L of catalyst A was put into the gap at 200 mL / min using a beaker simultaneously from each charging position, as in Example 1. Filled. After filling, the height of the catalyst layer at positions 0 m, 0.25 m, 0.50 m, 0.75 m, and 1 m from the end of the heat transfer plate was measured.

  Of the measured catalyst layer height, the height of the catalyst layer at the measurement position of 0.25 m was 1.73 m, which was the highest. Using the height of the catalyst layer as a reference (maximum point), the difference in height of the catalyst layer at other measurement positions with respect to the height of the catalyst layer at the measurement position of 0.25 m was obtained. The results are shown in Table 3. At the measurement positions of 0 m, 0.50 m, and 1 m, the difference in the height of the catalyst layer at these measurement positions relative to the height of the catalyst layer at the measurement position of 0.25 m is the difference in the catalyst layer at the measurement position of 0.25 m. It did not fall within the range of 0.173 m, which is within 10% of the height of 1.73 m.

[Example 2]
A partition was placed in the gap between the heat transfer plates of the plate reactor at an interval of 0.5 m, and catalyst A was packed in one of the partitioned sections. When filling, the charging position was set to 0.17 m and 0.33 m from the end of the compartment, and the charging position was set to 0.17 m from both ends of the compartment and the distance between the charging positions was 0.16 m. . A total of 12.4 L of catalyst was charged into the compartment at 200 mL per minute using a beaker simultaneously from each charging position. The height of the catalyst layer at positions 0 m, 0.17 m, 0.25 m, 0.33 m, and 0.50 m from the edge of the compartment was measured.

Of the measured catalyst layer height, the height of the catalyst layer at the measurement position of 0.17 m was 1.73 m, which was the highest. Using the height of the catalyst layer as a reference (maximum point), the difference in height of the catalyst layer at other measurement positions with respect to the height of the catalyst layer at the measurement position of 0.17 m was obtained. The results are shown in Table 4. At each measurement position, the difference of the height of the catalyst layer at the other measurement position with respect to the height of the catalyst layer at the measurement position of 0.17 m is 10 times the height of the catalyst layer of 1.73 m at the measurement position of 0.17 m. It was within the range of 0.173 m which is within%.

[Comparative Example 2]
A partition was placed in the gap between the heat transfer plates of the plate reactor at an interval of 0.5 m, and catalyst A was packed in one of the partitioned sections. At the time of filling, the charging position is set to a position of 0.25 m from one end of the section, the charging position is set to be 0.25 m from both ends, and 200 mL per minute from this charging position using a beaker. A total of 11.9 L of catalyst was charged into the compartment. The height of the catalyst layer was measured at 0 m, 0.25 m, and 0.50 m from the edge of the compartment.

  The height of the catalyst layer at the measurement position is 1.73 m, and the height of the catalyst layer at another measurement position with respect to the height of the catalyst layer at the measurement position with reference to the height of the catalyst layer as a reference (maximum point). The difference was calculated. The results are shown in Table 5. At the measurement positions of 0 m and 0.50 m, the difference in the height of the catalyst layer at these measurement positions with respect to the height of the catalyst layer at the measurement position of 0.25 m is the height of the catalyst layer at the measurement position of 0.25 m. It did not fall within the range of 0.173 m which is within 10% of 1.73 m.

[Example 3]
Catalyst A was filled in the gap between the heat transfer plates of the plate reactor. The filling was performed by using a filling device having a width of 0.10 m as shown in FIG. 15 instead of the beaker.

  The charging position is set to a position of 0.116 to 0.216 m, 0.450 to 0.550 m, and 0.784 to 0.884 m from one end of the gap, and a total of 25 at 200 mL / min from each charging position at the same time. 1 L of catalyst was filled into the gap. The heights of the catalyst layers at positions of 0 m, 0.166 m, 0.333 m, 0.500 m, 0.666 m, 0.834 m, and 1 m from the end of the gap were measured.

Of the measured catalyst layer height, the height of the catalyst layer at the measurement position of 0.500 m was 1.73 m, which was the highest. Using the height of the catalyst layer as a reference (maximum point), the difference in height of the catalyst layer at other measurement positions with respect to the height of the catalyst layer at the measurement position of 0.500 m was determined. The results are shown in Table 6. At each measurement position, the difference in the height of the catalyst layer at the other measurement position with respect to the height of the catalyst layer at the measurement position of 0.500 m is 10 times the height of the catalyst layer of 1.73 m at the measurement position of 0.500 m. It was within the range of 0.173 m which is within%.

[Comparative Example 3]
Catalyst A was filled in the gap between the heat transfer plates of the plate reactor using the same filling equipment as in Example 3. The charging position is set to a position of 0.2 to 0.3 m and 0.7 to 0.8 m from the end of the gap, and a total of 24.3 L of catalyst is simultaneously added to the gap at 200 mL / min from each charging position. Filled. The heights of the catalyst layers at positions of 0 m, 0.25 m, 0.50 m, 0.75 m, and 1 m from the end of the gap were measured.

  Of the measured catalyst layer height, the height of the catalyst layer at the measurement position of 0.25 m was 1.73 m, which was the highest. Based on the height (maximum point) of this catalyst layer, the difference in height of the catalyst layer at other measurement positions with respect to the height of the catalyst layer at the measurement position of 0.25 m was determined. The results are shown in Table 7. At the measurement positions of 0 m, 0.50 m, and 1 m, the difference in the height of the catalyst layer at these measurement positions relative to the height of the catalyst layer at the measurement position of 0.25 m is the difference in the catalyst layer at the measurement position of 0.25 m. It did not fall within the range of 0.173 m, which is within 10% of the height of 1.73 m.

[Example 4]
Catalyst B was filled in the gap between the heat transfer plates in the plate reactor. The positions of 0.125 m, 0.375 m, 0.625 m, and 0.875 m along the axial direction of the heat transfer tube from the end of the heat transfer plate are set as input positions (that is, the distance from the both ends of the heat transfer plate to the closest input position) Is set to 0.125 m, and the other charging positions are set to a distance of 0.25 m), and each charging position is set so that the maximum height of the packed bed is 1.73 m. At the same time, a total of 25.0 L of catalyst was filled in the gap at 200 mL per minute using a beaker. After filling, measure the height of the catalyst layer at 0m, 0.125m, 0.250m, 0.375m, 0.500m, 0.625m, 0.750m, 0.875m, 1m from the edge of the heat transfer plate did.

  Of the measured catalyst layer height, the height of the catalyst layer at the measurement position of 0.875 m was 1.73 m, which was the highest. Using the height of the catalyst layer as a reference (maximum point), the difference in height of the catalyst layer at other measurement positions with respect to the height of the catalyst layer at the measurement position of 0.875 m was obtained. The results are shown in Table 8. At each measurement position, the difference in the height of the catalyst layer at the other measurement position with respect to the height of the catalyst layer at the measurement position of 0.875 mm is 10 times the height of the catalyst layer of 1.73 m at the measurement position of 0.875 m. It was within the range of 0.173 m which is within%.

[Comparative Example 4]
Catalyst B was filled in the gap between the heat transfer plates in the plate reactor. Positions 0.17 m, 0.50 m, and 0.83 m along the axial direction of the heat transfer tube from the end of the heat transfer plate are set as input positions (that is, the distance from both ends of the heat transfer plate to the closest input position is 0.17 m) , Set the charging position so that the distance between other charging positions adjacent to each other is 0.33 m), and simultaneously beaker from each charging position so that the height of the highest point of the packed bed is 1.73 m Used to fill the gap with a total of 24.2 L of catalyst at 200 mL per minute. After filling, the height of the catalyst layer was measured at 0 m, 0.170 m, 0.335 m, 0.500 m, 0.665 m, 0.830 m, and 1 m from the end of the heat transfer plate.

  Of the measured catalyst layer height, the height of the catalyst layer at the measurement position of 0.500 m was 1.73 m, which was the highest. Using the height of the catalyst layer as a reference (maximum point), the difference in height of the catalyst layer at other measurement positions with respect to the height of the catalyst layer at the measurement position of 0.500 m was determined. The results are shown in Table 9. At the measurement positions of 0 m, 0.335 m, 0.665 and 1 m, the difference in the height of the catalyst layer at these measurement positions with respect to the height of the catalyst layer at the measurement position of 0.500 m is the measurement position at 0.500 m. The catalyst layer height was not within the range of 0.173 m, which is within 10% of the height of 1.73 m.

  From the above examples and comparative examples, when the catalyst is filled in the gap from a plurality of positions satisfying the expressions (1) and (2), the height difference of the catalyst layer in the axial direction of the heat transfer tube Can be reduced and the catalyst layer can be uniformly filled, while filling the gap from a position not satisfying the formula (1) and the formula (2), in the axial direction of the heat transfer tube, It was found that the difference in height of the catalyst layer became large and the catalyst was not uniformly packed.

  The gap between the heat transfer plates in the plate reactor is generally small and has a flat and complicated shape. For this reason, it is generally difficult to check or correct the filling state in filling the gap between the heat transfer plates. However, according to the present invention, the filling of the gap into the gap between the heat transfer plates is prevented. Since it can be carried out properly and its appropriate filling state can be easily determined, it is expected to improve workability in periodic work of plate reactors such as safety inspection work. In the production of a product using a reactor, further improvement in long-term productivity including such a regular operation is expected.

DESCRIPTION OF SYMBOLS 1 Heat transfer plate 2 Catalyst layer 3 Gas inlet 4 Gas outlet 5, 5-1, 5-2, 5-3 Heat transfer pipe 6 Casing 7 Partition 8 Vent plug 9 Perforated plate 10, 10 'Vents 11, 11' Casing End 12 Jacket 13 Circulating flow path 14 Pump 15 Heat exchanger 16 Nozzle 17 Distribution pipe 18 Window 19 Ventilation plate 20 First skirt portion 21 Second skirt portion 22 Locking window 23 Locking claw 31 Plates 32, 37 Frame 33 Handle 34 Guide plate 35 Hopper 36 Conveying surface 38 Restricting member 39 Belt conveyor 40 Vibrator 41 Partition plate 42 Dividing plate 43 Funnel 44 Supply pipe 45 Elbow P Distance between the axes of the pair of heat transfer plates L Waveform cycle length H Waveform height

Claims (7)

A reaction vessel for reacting raw materials, and a plurality of heat transfer plates provided side by side in the reaction vessel,
The heat transfer plate includes a plurality of heat transfer tubes connected at a peripheral edge or an edge of a cross-sectional shape, and is provided in the reaction vessel so that the heat transfer tubes are connected in a vertical direction.
A packing method for packing in a plate reactor, in which a particulate packing is introduced into a gap between adjacent heat transfer plates to form a packed bed in the gap,
A section where a packed bed is formed in the gap when the filler is filled into the gap from one charging position is a filling section, and the repose angle of the filler is θ (°), and the axial direction of the heat transfer tube Where B (m) is the distance from the charging position of the packing material to the end of the packing section, and E (m) is 10% of the set height of the highest point of the packed bed. 1) A method for filling a packing material in a plate reactor, wherein the packing material is charged into the gap so as to satisfy 1).
B ≦ E / tan θ (1) A method of filling the filling material into one filling section from a plurality of positions in the axial direction of the heat transfer tube,
2. The plate type according to claim 1, wherein when the distance between adjacent charging positions is A (m), the filler is charged into the gap so as to satisfy the following formula (2). Packing method of the packing material in the reactor.
A ≦ 2 × E / tan θ (2) The plate reactor further includes a partition that is arranged along the vertical direction in the gap and divides the gap in the vertical direction,
The method for filling a packing material in a plate reactor according to claim 1 or 2, wherein the packing section is a section formed by the partition.   The length of the said packing section in the axial direction of the said heat exchanger tube is 0.05m-2m, The packing method of the packing in the plate type reactor as described in any one of Claims 1-3 characterized by the above-mentioned.   The method for filling a packing material in a plate reactor according to any one of claims 1 to 4, wherein the packing material is one or both of a particulate catalyst and inert particles. A plate type having a plurality of heat transfer plates provided side by side in a reaction vessel for reacting raw materials, and including a plurality of heat transfer tubes in which the heat transfer plates are connected in the vertical direction at the periphery or edge of the cross-sectional shape A method of producing a reaction product from a raw material by a catalytic reaction using a reactor, the step of passing the raw material through a catalyst layer formed by dropping the catalyst into a gap between adjacent heat transfer plates; Supplying a heat medium having a desired temperature to the heat transfer tube,
The raw material is at least one selected from the group consisting of ethylene; hydrocarbons having 3 and 4 carbon atoms and tertiary butanol, or at least one selected from the group consisting of unsaturated aliphatic aldehydes having 3 and 4 carbon atoms. An aliphatic hydrocarbon having 4 or more carbon atoms, o-xylene, an olefin, a carbonyl compound, cumene hydroperoxide, butene, or ethylbenzene;
The obtained reaction product is ethylene oxide; at least one of unsaturated aliphatic aldehydes having 3 and 4 carbon atoms and unsaturated fatty acids having 3 and 4 carbon atoms; maleic acid; phthalic acid; paraffin; alcohol; acetone and phenol; Butadiene; or styrene;
A method for producing a product, wherein the plate reactor according to any one of claims 1 to 5 is used for the plate reactor.   The raw material is propylene or isobutylene, and propylene or isobutylene is oxidized using a molecular oxygen-containing gas to produce one or both of (meth) acrolein and (meth) acrylic acid. The manufacturing method as described.

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