WO2009123151A1

WO2009123151A1 - Plate type reactor, manufacturing method therefor, and reaction product manufacturing method using the plate type reactor

Info

Publication number: WO2009123151A1
Application number: PCT/JP2009/056567
Authority: WO
Inventors: 真治磯谷; 公克神野; 康之坂倉; 洋治川谷; 修平矢田
Original assignee: 三菱化学株式会社; 三菱化学エンジニアリング株式会社
Priority date: 2008-03-31
Filing date: 2009-03-30
Publication date: 2009-10-08
Also published as: RU2489203C2; RU2010144507A; CN104707540A; CN101977678A; CN104803834A

Abstract

In a plate type reactor, there are provided a technique for preventing the runaway of a reaction in the manufacture of a reaction product and for manufacturing the reaction product in a high productivity, a technique for filling the clearance between adjoining heat transfer plates in the plate type reactor, at least homogeneously and easily with a catalyst, and a method for suppressing the pressure loss, the occurrence of a hot spot and the loss of the catalyst even in the run under a high-load condition, thereby to manufacture the reaction product in a high efficiency in the plate type reactor. The reaction product is manufactured by arranging the heat transfer plates of the plate type reactor within a specified range of errors from a designed value, by arranging a plurality of partitions for forming a plurality of compartments in the clearances between the heat transfer plates and along the flow direction of a reaction material, by further arranging a plurality of vent plugs for plugging the bottom portions of the individual partitions removably, and by using a specific reaction material under the condition of a specific quantity of load.

Description

Plate reactor, method for producing the same, and method for producing a reaction product using the plate reactor

The present invention relates to a plate reactor used for a reaction involving heat generation or endotherm using a catalyst, a method for producing the same, and a method for producing a reaction product by a gas phase contact reaction using the plate reactor.

The present invention also relates to a plate reactor and a production method for producing a reaction product by supplying a reaction raw material to a plate reactor filled with a catalyst and reacting the reaction raw material.

As a reactor used in a gas phase catalytic reaction for obtaining a gaseous reaction product by reacting a gaseous raw material in the presence of a solid catalyst, for example, a reaction tube in a reaction vessel is filled with the catalyst. A multi-tubular reactor (see, for example, Patent Document 1) and a plate reactor in which a catalyst is filled in a gap between a plurality of heat transfer plates in a reaction vessel (see, for example, Patent Documents 2 and 3). ,It has been known.

These reactors used for the gas phase contact reaction are generally required to be manufactured with high accuracy. For example, if there is a large error in the tube diameter of the heat transfer tubes that make up the reaction tubes in a multi-tube reactor or a heat transfer plate in a plate reactor, a part of the catalyst layer that is poor in heat removal will react. May run away and the catalyst may deteriorate locally. However, if an attempt is made to produce a reactor with higher accuracy, production of the reactor may require a great deal of labor and a large amount of steel.

In a multi-tubular reactor, the accuracy of the reactor can be increased relatively easily by using a highly accurate steel pipe for the reaction tube. On the other hand, a heat transfer tube in a plate reactor is generally manufactured by forming a steel plate so that a plurality of shapes obtained by dividing the cross-sectional shape of the heat transfer tube are continuous, and welding convex edges of the formed steel plate. In the plate reactor, the cross-sectional shape and the cross-sectional size of the heat transfer tube are generally determined from the viewpoint of adjusting the thickness and form of the catalyst layer formed in the gap between the heat transfer plates. Therefore, in the production of the plate-type reactor, when the desired shape is not obtained in the forming of the steel plate, when the formed steel plate is warped, and when the warpage is caused by welding of the steel plate, etc. Due to various factors that reduce the accuracy of the plate reactor, it is difficult to manufacture a plate reactor with high accuracy, and thus the reaction may not be sufficiently controlled.

Thus, the form and manufacturing method of the heat transfer plate in the plate reactor makes it difficult to manufacture the plate reactor with high accuracy. In a plate heat exchanger having a structure similar to a plate reactor in that it has a heat transfer plate composed of heat transfer tubes, the maximum error for the set value of the distance between the heat transfer plates is usually 3-5 mm. It is said to be more or less.

However, it is important to strictly control the reaction temperature in a gas phase catalytic reaction involving exotherm or endotherm using a catalyst. If the temperature of the catalyst layer is insufficiently controlled, the catalyst may deteriorate or the yield of the target reaction product may decrease. Therefore, if the accuracy of the plate reactor is low, for example, if the error with respect to the set value of the distance between the heat transfer plates is large, a part of the heat removal is partially made, and the reaction runs away in a part of the catalyst layer, The catalyst may deteriorate locally and the yield of the reaction product may decrease. On the other hand, if emphasis is placed on improving the accuracy of the plate reactor, a great deal of labor and a large amount of steel are required to produce the plate reactor, which reduces the productivity in the production of reaction products using such a reactor. In some cases, it may become impractical for industrial production of reaction products.

As a reactor used in a gas phase reaction in which a granular solid catalyst is used, such as a gas phase catalytic oxidation reaction of propane, propylene, or acrolein, and a granular solid catalyst is used, for example, a gaseous reaction raw material is reacted. A reaction vessel, a plurality of heat transfer plates provided side by side in the reaction vessel, and a device for supplying a heat medium to the heat transfer tube, wherein the reaction vessel is supplied The gas is discharged through a gap between adjacent heat transfer plates, and the heat transfer plate includes a plurality of the heat transfer tubes connected at the peripheral edge or the edge of the cross-sectional shape. There is known a plate reactor in which a catalyst is filled in a gap between matching heat transfer plates (see, for example, Patent Document 3).

Such a plate reactor generally has a plurality of catalyst layers formed in the gaps between adjacent heat transfer plates and has excellent contact between the heat transfer plates and the catalyst. It is excellent from the viewpoint of efficiently producing a product by a phase reaction in a large amount.

On the other hand, in the gas phase reaction, it is desired to make the packing state of the catalyst uniform from the viewpoint of controlling the gas phase reaction. In a plate reactor, the gap between adjacent heat transfer plates is filled with a catalyst in layers, so it is difficult to fill each gap and the catalyst uniformly, and the gap is filled uniformly with the catalyst. A technology that can do this has been desired.

Further, when the catalyst was not filled in the gap uniformly, or when a part of the catalyst in the gap deteriorated, it was necessary to take out the catalyst in the whole gap and refill the catalyst. For this reason, the technique which can adjust the filling state of the catalyst in the said clearance gap easily was desired.

At present, in a production method for producing a reactant such as an unsaturated fatty acid by using a catalytic gas phase oxidation reaction, a multi-tubular reactor having a tubular heat exchanger shape is used from an industrial and practical viewpoint. ing. In the method for producing a reactant using the multitubular reactor, a solid catalyst is filled inside the reaction tube of the multitubular reactor, and a temperature-controlled heat medium is circulated outside the reaction tube. The temperature inside the reaction tube is controlled by the heat medium.

When producing reactants such as unsaturated fatty acids using the above multi-tubular reactor, it is necessary to increase the number of reaction tubes according to the increase in the production amount when it is desired to increase the production amount of the reactant. . However, in this case, the number of reaction tubes may reach tens of thousands, which may exceed the production limit of multi-stage reactors. When the production limit is exceeded, the reality is that you have to own multiple reaction sequences.

On the other hand, there is a case where a desired production amount is secured by increasing the processing load per unit catalyst with a specified number of reaction tubes or reactors. At this time, the reaction heat generated in each reaction tube increases, and a situation occurs in which the temperature inside the reaction tube cannot be appropriately controlled by the heat medium circulated outside the reaction tube. When the temperature inside the reaction tube cannot be appropriately controlled, the temperature of a part of the catalyst held inside the reaction tube rises remarkably (hereinafter also referred to as a hot spot). If the temperature of a part of the catalyst exceeds the limit, a part of the catalyst is damaged and the useful life of the catalyst is shortened.

When a part of the catalyst is damaged, production of the reactant using the reactor is stopped, and the catalyst needs to be replaced. That is, while the catalyst is exchanged, production of reactants is stopped, and serious problems such as difficulty in securing a desired production amount occur. Even if the catalyst is not replaced, the occurrence of hot spots makes it difficult to maintain appropriate reaction conditions, resulting in problems such as a deterioration in the reaction performance of the catalyst and a decrease in the yield of the target reactant.

Patent Documents

4 and 5 propose a method in which a catalytic gas phase oxidation reaction of propylene and acrolein, which are reaction raw materials, is carried out with an increased processing load per unit catalyst using the multi-tubular reactor. Yes. However, the reaction tube used in the multi-tube reactor is a pipe having a radius of 20 to 30 millimeters, and a reaction tube having the same diameter from the inlet to the outlet of the reaction fluid (a general term for a reaction raw material mixture and a reaction product mixture). Therefore, under conditions where the processing load per unit catalyst of the reaction fluid is high, the pressure loss of the reaction fluid is large, the pressure in the reactor rises, and as a result, the yield of the target reactant decreases. is there. Further, as the internal pressure of the reactor increases, the energy of the compressor for supplying the reaction fluid and the like increases, which is disadvantageous in terms of cost in addition to the yield of the target reactant.

As one method for solving the above problems, a reactor for catalytic gas phase oxidation having a plate heat exchanger structure has been proposed. For example, Patent Document 2 proposes a plate-type catalytic reaction apparatus in which a catalyst is filled between two heat transfer plates and a heat medium is supplied to the outside of the heat transfer plate. Further, in Patent Document 3, a heat transfer plate in which a plurality of corrugated plates formed into an arc or an elliptical arc face each other and the convex portions of the corrugated plates are joined to each other to form a plurality of heat medium channels is provided. A plate-type catalytic reactor in which a plurality of arrayed and adjacent corrugated convex portions and concave portions of adjacent heat transfer plates face each other to form a catalyst layer at a predetermined interval has been proposed.

The above proposal describes the structure of the plate reactor and its application to the catalytic gas phase oxidation reaction. However, the yield of the target reactant is reduced while appropriately controlling the heat generated by the reaction to prevent hot spots. There is no mention of how to improve. In particular, when the processing load per unit catalyst is increased, heat generated by the reaction is appropriately controlled to prevent hot spots, damage to the catalyst, and the yield and production amount of the target reactant are improved. There is no mention about.

Japanese Unexamined Patent Publication No. 2004-000944 Japanese Unexamined Patent Publication No. 2004-167448 Japanese Unexamined Patent Publication No. 2004-202430 Japanese National Table 2003-514788 Japan Special Table 2002-539103 Publication

The present invention provides a plate reactor that can prevent reaction runaway in the production of a reaction product and can be used for production of a reaction product with high productivity.

In addition, the present invention provides a method for preventing reaction runaway and producing a reaction product with high productivity in the production of a reaction product using a plate reactor.

The present invention also provides a plate reactor that can uniformly and easily fill the gaps between adjacent heat transfer plates.

The present invention also provides a plate reactor in which the gap between adjacent heat transfer plates can be uniformly and easily filled with the catalyst, and the filling state of the catalyst in the gap can be easily adjusted. .

Furthermore, the present invention increases the processing load of a reaction raw material per unit catalyst in a production method in which a reaction raw material is supplied to a plate reactor filled with a catalyst and the reaction raw material is reacted to produce a reaction product. Even if it is, the target reaction can be generated while preventing an increase in the pressure loss of the reaction gas passing through the catalyst and preventing the hot spot by properly controlling the heat generated by the reaction, preventing the catalyst from being damaged. The object is to provide a novel method for improving the yield of the product.

In the present invention, the temperature range of the plate reactor is controlled by setting the allowable error range to -0.6 to +2.0 mm with respect to the design value of the distance between the surfaces of the heat transfer plates. The present invention provides a technology for producing a valuable material by an industrially advantageous method while maintaining the production cost of a plate reactor at a low cost without depending on the use of a low activity catalyst or dilution of the catalyst.

That is, the present invention provides a reaction vessel for reacting a gaseous raw material, a plurality of heat transfer plates provided side by side in the reaction vessel, and a heat for supplying a heat medium at a desired temperature to the heat transfer plate. 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 the heat medium supply device is a heat transfer plate accommodated in a reaction vessel In the plate reactor that is a device for supplying a heat transfer medium to the heat transfer tube, a gap between the heat transfer plates facing each other is transferred in a direction perpendicular to a surface that is equidistant from the surface formed by the axis of the heat transfer plate. The design value of the distance between the surfaces of the heat plate is 5 to 50 mm, and the difference of the measured value of the distance between the surfaces with respect to the design value is −0.6 to +2.0 mm (hereinafter, “ First plate reaction Also referred to) to provide a ".

The present invention also provides a first plate reactor in which the heat transfer plate has an axial length of preferably 5 m or less, more preferably 2 m or less.

Also, the present invention preferably provides a first plate reactor that further includes a spacer for forming a predetermined interval between the heat transfer plates.

In the present invention, it is preferable that the heat transfer plate is formed by joining two steel plates formed so that a plurality of shapes obtained by dividing the cross-sectional shape of the heat transfer tube into two by the shaft of the heat transfer plate are continuous. A plate reactor is provided.

In the present invention, it is preferable that the first plate reactor in which the difference in the measured value of the distance between the surfaces with respect to the design value is smaller on the upstream side in the flow direction of the raw material gas in the gap between the heat transfer plates is smaller. provide.

In the present invention, it is preferable that the difference in the measured value of the distance between the surfaces with respect to the design value at a position where the reaction rate of the raw material in the raw material gas is 70% or less is a position where the reaction rate is greater than 70%. The first plate reactor is smaller than the difference between the measured values of the distance between the surfaces with respect to the design value at.

Also, the present invention preferably provides a first plate reactor in which the total volume of the gap is 3 L or more.

In addition, the present invention preferably provides a first plate reactor that further includes a temperature measuring device for measuring temperatures at two or more positions of the catalyst layer in which the gap is filled with a catalyst.

Further, the present invention uses a plate reactor in which a plurality of heat transfer plates are provided side by side in a reaction vessel, and a catalyst layer is formed by filling a catalyst between gaps between the heat transfer plates. The raw material gas is reacted in the presence of the catalyst, including a step of supplying the raw material and passing through the catalyst layer, and a step of supplying a heat medium having a predetermined temperature to the plurality of heat transfer tubes constituting the heat transfer plate. In the method for producing a reaction product that generates a gaseous reaction product, the plate reactor of the present invention is used for the plate reactor, and the peak temperature of the catalyst layer is set when the plate reactor is designed. Provided is a method for producing a reaction product (hereinafter, also referred to as “first production method for reaction product”) in which a heat medium having a temperature set to the peak temperature of the catalyst layer is supplied to the heat transfer tube.

In addition, the present invention preferably provides a first method for producing a reaction product in which the reaction of the raw material in the raw material gas in the presence of a catalyst is an exothermic reaction.

In the present invention, it is preferable that the reaction product is one or both of acrolein and acrylic acid, one or both of methacrolein and methacrylic acid, maleic acid, phthalic acid, ethylene oxide, paraffin, alcohol, acetone and phenol, Alternatively, a first method for producing a reaction product that is butadiene is provided.

Furthermore, the present invention provides a reaction vessel for reacting a gaseous raw material, a plurality of heat transfer plates provided side by side in the reaction vessel, and a heat medium supply for supplying a heat medium of a desired temperature to the heat transfer plate And 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 the heat medium supply device includes a heat transfer plate accommodated in a reaction vessel. In a method of manufacturing a plate reactor that is a device for supplying a heat medium to a heat pipe, the heat transfer in a direction perpendicular to a surface that is equidistant from the surface formed by the axis of the heat transfer plate in the gap between the opposed heat transfer plates. Provided is a plate reactor manufacturing method including a step of arranging a heat transfer plate at an interval where a distance between surfaces of a heat plate is a design value and joining a heat transfer tube and a heat medium supply device.

In the present invention, it is preferable that the heat transfer plate is formed by joining two steel plates formed such that a plurality of shapes obtained by dividing the cross-sectional shape of the heat transfer tube into two by the shaft of the heat transfer plate are continuous. Provided is a method for producing the plate reactor using a formed steel plate, wherein the steel plate formed using a hot plate has an error of ± 0.5 mm or less with respect to a design value for forming the steel plate.

Alternatively, the present invention preferably provides a method for producing the plate reactor, wherein the heat transfer plate is a heat transfer plate having an axial length of 5 m or less, preferably 2 m or less. To do.

In the present invention, it is preferable that the distance between the surfaces of the heat transfer plates is transferred to the reaction container before joining with the heat transfer medium supply device via a spacer that forms an interval between the heat transfer plates. A method for manufacturing the plate reactor is further provided, further comprising the step of arranging a hot plate.

In the present invention, preferably, a plurality of compartments capable of accommodating the catalyst are formed in the gaps between adjacent heat transfer plates in the plate reactor along the flow direction of the reaction raw material, Provided is a plate reactor that can be packed uniformly with a catalyst.

In the present invention, preferably, a plurality of compartments capable of accommodating the catalyst are formed in the gap between adjacent heat transfer plates in the plate reactor along the flow direction of the reaction raw material. A plate reactor capable of charging and discharging the catalyst independently.

That is, the present invention comprises a reaction vessel for reacting reaction raw materials, a heat transfer tube, a plurality of heat transfer plates provided side by side in the reaction vessel, a device for supplying a heat medium to the heat transfer tube, The reaction vessel is a vessel in which the supplied reaction raw material is discharged through a gap between adjacent heat transfer plates, and the heat transfer plate is connected at a peripheral edge or an edge of a cross-sectional shape. In the plate reactor in which the catalyst is filled in the gap between the adjacent heat transfer plates, the gap between the adjacent heat transfer plates is arranged along the ventilation direction in the reaction vessel. Provided is a plate reactor (hereinafter, also referred to as “second plate reactor”) further having a partition for dividing a packed catalyst into a plurality of compartments.

The present invention preferably also provides a second plate reactor in which the volumes of the plurality of compartments are the same.

In addition, the present invention preferably provides a second plate reactor in which the volume of each of the plurality of compartments is 1 to 100 L.

In addition, the present invention preferably provides a second plate reactor in which the volume of each of the plurality of compartments is 2 to 25 L.

Further, the present invention preferably includes a plurality of vent plugs that are breathable, are detachably fixed to the end portions of the respective compartments, and block the end portions of the respective compartments so as to hold the catalyst accommodated in the respective compartments. A second plate reactor is further provided.

In the present invention, it is preferable that one or both of the partition and the heat transfer plate have a first locking portion for locking the vent plug, and the vent plug has air permeability and a catalyst. A ventilation plate that does not pass through, a skirt portion that is provided perpendicularly to the ventilation plate at a part or all of the periphery of the ventilation plate, and a detachable engagement with the first locking portion provided in the skirt portion A second plate reactor having a second locking portion.

Also, the present invention preferably provides a second plate reactor in which the interval between the plurality of partitions is 0.1 to 1 m.

The present invention is preferably a method for producing a reaction product using a second plate reactor,
Supplying a heat medium having a desired temperature to the heat transfer tube, supplying a reaction raw material to a gap between adjacent heat transfer plates filled with a catalyst, and obtaining a reaction product discharged from the gap; Including
The reaction 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 1 selected from the group consisting of unsaturated aliphatic aldehydes having 3 and 4 carbon atoms. Species; hydrocarbons having 4 or more carbon atoms; xylene and / or naphthalene; olefins; carbonyl compounds; cumene hydroperoxide; butenes;
The 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; Or styrene (hereinafter, also referred to as “second production method of reaction product”).

Furthermore, the present inventors have intensively studied to solve the above problems, and the plate-type reaction is divided into a plurality of reaction zones in which the average layer thickness of the catalyst layer formed between the heat transfer plates is different. In the production method of supplying a reaction raw material to a reactor, catalytic vapor phase oxidation of the reaction raw material, and producing a target reaction product, paying attention to the temperature of the heat medium supplied to the plurality of reaction zones, the present invention It came to be completed. That is, the gist of the present invention is as follows.

That is, the present invention
(A) a plate reactor having a catalyst layer formed between heat transfer plates, at least one reaction raw material selected from the group consisting of hydrocarbons having 3 and 4 carbon atoms and tertiary butanol; and Supplying a reaction raw material mixture containing molecular oxygen, catalytic vapor phase oxidation of the reaction raw material, and at least one selected from the group consisting of unsaturated hydrocarbons and unsaturated aliphatic aldehydes having 3 and 4 carbon atoms Producing a reaction product, or
(B) A production method using a plate reactor provided with a catalyst layer formed between heat transfer plates, wherein at least a reaction raw material selected from the group consisting of unsaturated aliphatic aldehydes having 3 and 4 carbon atoms A reaction raw material mixture containing one kind and molecular oxygen is supplied, and the reaction raw material is subjected to catalytic gas phase oxidation to produce at least one reaction product selected from the group consisting of unsaturated fatty acids having 3 and 4 carbon atoms. In the way to
The plate reactor is divided into a plurality of reaction zones having different average layer thicknesses of the catalyst layers, and a heat medium whose temperature is independently adjusted is supplied to the plurality of reaction zones. The heat generated is removed through the heat transfer plate, and the temperature in the catalyst layer is independently controlled,
The temperature T (S1) of the heating medium supplied to the reaction zone S1 closest to the inlet of the reaction raw material mixture is adjacent to the reaction zone S1 and is located downstream of the flow of the reaction raw material mixture. Higher than the temperature T (S2) of the heat medium supplied to
The load of the reaction raw material when oxidizing at least one of the reaction raw materials selected from the group consisting of the hydrocarbons having 3 and 4 carbon atoms and tertiary butanol is 150 liters per hour per liter of catalyst [standard state (Temperature 0 ° C., 101.325 kPa) conversion]
When oxidizing at least one kind of the reaction raw material selected from the group consisting of the unsaturated aliphatic aldehydes having 3 and 4 carbon atoms, the loading amount of the reaction raw material is 160 liters per hour per 1 liter of catalyst [standard state (temperature One or more reactions selected from the group consisting of unsaturated hydrocarbons, unsaturated aliphatic aldehydes having 3 and 4 carbon atoms, and unsaturated fatty acids having 3 and 4 carbon atoms. A production method for producing a product (hereinafter also referred to as “third production method of a reaction product”) is provided.

In the present invention, preferably, the temperature of the heat medium supplied to any unspecified reaction zone S (j) is T (Sj), adjacent to the reaction zone S (j), and the flow of the reaction raw material mixture When the temperature of the heat medium supplied to the reaction zone S (j + 1) located downstream is T (Sj + 1), T (Sj) and T (Sj + 1) are T (Sj) −T (Sj + 1) )> 5, a third method for producing a reaction product is provided.

In the present invention, preferably, the number of the reaction zones is 2 to 5, and the average layer thickness of the catalyst layer in each reaction zone increases from the reaction raw material mixture inlet to the outlet. A third manufacturing method is provided.

In the present invention, preferably, the amount of the reaction raw material loaded when oxidizing at least one of the reaction raw materials selected from the group consisting of the hydrocarbons having 3 and 4 carbon atoms and tertiary butanol is the catalyst 1 A third method for producing a reaction product is provided which is 170 to 290 liters per liter per hour [converted to a standard state (temperature 0 ° C., 101.325 kPa)].

In the present invention, it is preferable that the amount of the reaction raw material loaded per liter of the catalyst when oxidizing at least one of the reaction raw materials selected from the group consisting of the above-mentioned unsaturated aliphatic aldehydes having 3 and 4 carbon atoms. A third method for producing a reaction product, which is 180 to 300 liters per hour [converted to a standard state (temperature 0 ° C., 101.325 kPa)], is provided.

Also, the present invention preferably provides a third method for producing a reaction product, wherein the conversion rate of the reaction raw material at the reaction product outlet of the plate reactor is 90% or more.

In the present invention, preferably, the reaction raw material is propylene, and the temperature of the heat medium supplied to the plurality of reaction zones is 320 to 400 ° C., or the reaction raw material is acrolein, A third method for producing a reaction product is provided, wherein the temperature of the heat medium supplied to the reaction zone is 250 to 320 ° C.

In the first plate reactor, the measured value of the distance between the surfaces of the heat transfer plate in the plate reactor is included in the specific range described above with respect to the design value. It is possible to control without causing the reaction to runaway, and a plate reactor capable of such control can be manufactured without much labor and use of a large amount of steel. A reactor can be obtained.

In the first plate reactor, the length of the heat transfer plate in the axial direction is 5 m or less, preferably 2 m or less. It is more effective from the viewpoint of obtaining a small plate reactor.

The first plate reactor further includes a spacer for forming a predetermined interval between the heat transfer plates, so that the difference between the measured values with respect to the design value of the distance between the surfaces of the heat transfer plates is small. It is much more effective from the viewpoint of obtaining a plate reactor.

In the first plate reactor, the heat transfer plate is formed by joining two steel plates formed so that a plurality of shapes obtained by dividing the cross-sectional shape of the heat transfer tube into two by the shaft of the heat transfer plate are continuous. This is even more effective from the viewpoint of reducing the difference between the measured values with respect to the design value of the distance between the surfaces of the heat transfer plates.

Further, in the first plate reactor, the difference in the measured value of the distance between the surfaces with respect to the design value is smaller on the upstream side in the flow direction of the raw material gas in the gap between the heat transfer plates. The difference in the measured value of the distance between the surfaces with respect to the design value at a position where the reaction rate of the raw material in the raw material gas is 70% or less is more effective from the viewpoint of increasing the accuracy of the reaction gas. It is even more effective that it is smaller than the difference of the measured value of the distance between the surfaces with respect to the design value at a larger position.

In the first plate reactor, the total volume of the gaps between the heat transfer plates is 3 L or more, which is more effective from the viewpoint of producing the reaction product with high productivity.

The first plate reactor further includes a temperature measuring device for measuring temperatures at two or more positions of the catalyst layer in which a catalyst is filled in a gap between the heat transfer plates. This is even more effective from the viewpoint of increasing control accuracy.

Further, in the first production method of the reaction product, the reaction of the raw material in the raw material gas in the presence of the catalyst is an exothermic reaction, which is more effective from the viewpoint that the effect of the present invention is remarkably obtained. It is even more effective that the reaction product is one or both of acrolein and acrylic acid, one or both of methacrolein and methacrylic acid, maleic acid, phthalic acid, ethylene oxide, paraffin, alcohol, acetone and phenol, or butadiene. Is.

Further, in the first plate reactor production method, in the heat transfer plate, using a formed steel sheet having an error with respect to a design value of forming the steel sheet within ± 0.5 mm is actually measured with respect to the design value. This is even more effective from the viewpoint of reducing the difference in values.

In the first plate reactor manufacturing method, the heat transfer plates before joining are arranged through spacers that form a distance between the heat transfer plates so that the distance between the surfaces of the opposite heat transfer plates is a design value. This is more effective from the viewpoint of reducing the difference between the measured values and the design values.

Since the second plate reactor has the partition, it can be filled with an amount of catalyst corresponding to the capacity of each section formed by the partition, and the packing state of the catalyst is made constant in each section. Thus, the catalyst can be uniformly filled in the entire gap between adjacent heat transfer plates in the plate reactor. Thus, in the plate reactor of the present invention, the catalyst can be uniformly and easily filled in the gaps between the adjacent heat transfer plates as compared with the conventional plate reactor.

In the second plate reactor, it is more effective that the volume of each of the plurality of compartments is the same from the viewpoint of easily keeping the packed state of the catalyst in each compartment.

In the second plate reactor, the volume of each of the plurality of compartments is 1 to 100 L, which is more effective from the viewpoint of facilitating the catalyst filling operation in each compartment.

In the second plate reactor, the volume of each of the plurality of compartments is 2 to 25 L, which is more effective from the viewpoint of facilitating the catalyst filling operation in each compartment.

Further, in the second plate reactor, it is possible to further include the vent plug so that the catalyst filled in the gap between the adjacent heat transfer plates can be taken out in a unit of unit, and the gap between the adjacent heat transfer plates can be uniformly and easily. It is more effective from the viewpoint of easily filling the catalyst with the catalyst and easily adjusting the filling state of the catalyst in the gap.

In the second plate reactor, the first locking portion, the vent plate, the skirt portion, and the second locking portion have sufficient vent plugs at the end of each section. This is more effective from the viewpoint of fixing with strength and easy attachment / detachment of the vent plug.

In the second plate reactor, the interval between the plurality of partitions is 0.1 to 1 m, which is more effective from the viewpoint of facilitating the catalyst filling operation in each section.

In recent years, chemical products are often mass-produced in large-scale facilities, the reactors installed in the production facilities have become larger, and the amount of catalyst to be inserted has become large. Uniform and efficient filling is very important. In particular, in the case of a reaction where heat of reaction is generated or absorbed, and the temperature rise or drop due to the heat of reaction affects the reaction rate, reaction performance, and further the degree of deterioration of the catalyst, reaction raw materials such as gas and liquid and the catalyst are removed. Uniform contact is a critical issue in designing a better reactor.

In the second production method of the reaction product, 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 unsaturated fat having 3 and 4 carbon atoms. At least one selected from the group consisting of a group aldehyde; hydrocarbon having 4 or more carbon atoms; xylene and / or naphthalene; olefin; carbonyl compound; cumene hydroperoxide; butene; or ethylbenzene; At least one of C3 and C4 unsaturated aliphatic aldehyde and C3 and C4 unsaturated fatty acid; maleic acid; phthalic acid; paraffin; alcohol; acetone and phenol; butadiene; In some methods, using the plate reactor, Since the raw material is processed by uniformly filled catalyst between the heat transfer plates, it is more effective from the viewpoint of improving the heat removal or the heating method of the heat of reaction in such catalytic reaction.

In the third production method of the reaction product, a reaction raw material is supplied to a plate reactor filled with a catalyst, and the reaction raw material is reacted to produce a reaction product. The purpose is to prevent an increase in the pressure loss of the reaction fluid that passes through the catalyst when the processing load is increased, and to prevent hot spots by appropriately controlling the heat generated by the reaction, thereby preventing damage to the catalyst. It is possible to improve the yield of the reaction product.

FIG. 1 is a diagram schematically showing the configuration of a plate reactor according to an embodiment of the present invention. FIG. 2 is a cross-sectional view of the plate reactor of FIG. 1 taken along line A-A ′. FIG. 3 is a cross-sectional view of the plate reactor of FIG. 1 taken along line B-B ′. FIG. 4 is a diagram showing an example of the appearance of the plate reactor of FIG. FIG. 5 is a view showing dimensions of the heat transfer tube 1. FIG. 6 is a diagram illustrating an example of a heat medium mixing apparatus. FIG. 7 is a diagram illustrating an example of the partition 7. FIG. 8 is a diagram illustrating an example of the vent plug 8. FIG. 9 is a diagram illustrating an example of an installation state of the vent plug 8. FIG. 10 is a diagram illustrating an example of the temperature measuring device 9. FIG. 11 is a diagram illustrating an example of the catalyst layer formed in the gap between the heat transfer plates 2. FIG. 12 is a diagram schematically showing another form of the heat transfer plate. FIG. 13 is a diagram schematically showing the configuration of the second embodiment in the plate reactor of the present invention. FIG. 14 is a view showing a cross section of the plate reactor of FIG. 13 taken along line A-A ′. FIG. 15 is a view showing a cross section of the plate reactor of FIG. 13 taken along line B-B ′. FIG. 16 is a view showing adjacent heat transfer plates 2 and partitions 7 provided therebetween. FIG. 17 is a diagram illustrating an example of the partition 7. FIG. 18 is a diagram illustrating another example of the partition 7. FIG. 19 is a diagram illustrating another example of the partition 7. FIG. 20 is a diagram illustrating another example of the partition 7. FIG. 21 is a diagram illustrating another example of the partition 7. FIG. 22 is a diagram illustrating another example of the partition 7. FIG. 23 is a diagram schematically showing the configuration of the third embodiment in the plate reactor of the present invention. FIG. 24 is a view showing a cross section when the plate reactor of FIG. 23 is cut along the line A-A ′. FIG. 25 is a view showing a cross section of the plate reactor of FIG. 23 taken along line B-B ′. FIG. 26 is a diagram showing the partition 7. FIG. 27 is a view showing adjacent heat transfer plates 2 and a partition 7 and a vent plug 8 provided therebetween. FIG. 28 is a perspective view of the vent plug 8. FIG. 29 is a development view of the vent plug 8. FIG. 30 is a view showing a detachable structure between the vent plug 8 and the partition 7. FIG. 31 is a diagram illustrating an example of a tool used for removing the vent plug 8. FIG. 32 is a view showing another detachable structure of the vent plug 8 and the partition 7. FIG. 33 is a view showing another example of a vent plug used in the present invention. FIG. 34 is a view showing another example of a vent plug used in the present invention. FIG. 35 is a view showing another example of a vent plug used in the present invention. FIG. 36 is a view showing another example of a vent plug used in the present invention. FIG. 37 is a view showing another example of a vent plug used in the present invention. FIG. 38 is a view showing another example of a vent plug used in the present invention. FIG. 39 is a diagram showing another example of a vent plug used in the present invention and its detachable fixing configuration. FIG. 40 is a diagram showing another example of a vent plug used in the present invention and its detachable fixing configuration. FIG. 41 shows a longitudinal sectional view of the plate reactor. FIG. 42 shows a longitudinal sectional view of the plate reactor. FIG. 43 shows an enlarged view of the heat transfer plate.

Explanation of symbols

1, a to c

Heat transfer tubes

2 and 57 Heat transfer plate 3 Holding plate 4 Holding rod 5 Heat medium supply device 6 Gas distribution section 7 Partition 8 Vent plug 9

Temperature measuring device

10, 46

Perforated plate

11, 12

Jacket

13, 16 , 18 Nozzle 14 Heat exchanger 15 Pump 17 Distribution pipe 19 Manhole 20 Window 21 Ventilation plate 22 First skirt part 23 Second skirt part 24

Locking window

25, 50, 51 Locking claw 26 Support body 27 Temperature measurement part 28 Spacer rod 29 Flange 30 Connector 31 Cable 32 Fixing flange 33-35

Flow path

36, 43 Catalyst layer 37-39, 40-42 Reaction zone 44 Casing 45 Heat medium accommodating portion 47 Temperature adjusting device 48, 48 'Vent 49 49 ′ Casing end 52 First vent pipe 53 Second vent pipe 54 Flange portion 55 Fixing pin 56 Energizing member 58 Reaction gas inlet 59 Reaction gas outlet 60-1 Heat medium flow path 60-2 Heat medium flow path 60-3 Heat medium flow path 61 Heat medium supply port P Distance between a pair of heat transfer plates L Wave period H Wave height Y Arrow x indicating the direction of flow

<First plate reactor>
The first plate reactor includes a reaction vessel for reacting a gaseous raw material, a plurality of heat transfer plates provided side by side in the reaction vessel, and a heat medium having a desired temperature on the heat transfer plate. A heating medium supply device for supplying.

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 preferably a pressure-resistant vessel that can withstand an internal pressure of 3,000 kPa (kilopascal). As such a reaction container, for example, a shell in which a cylindrical portion or a part thereof is combined, 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 are accommodated. As described above, a container having a housing-like interior surrounded by members constituting the inner surface of the plane can be used.

The heat transfer plate includes a plurality of heat transfer tubes connected in the vertical direction at the peripheral edge or edge of the 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 joining two steel plates each formed into a shape in which the cross-sectional shape of the heat transfer tube is divided into two or more are directly or indirectly connected to each other. From the viewpoint of obtaining.

The interval between the heat transfer plates is set according to a design value, and may be an equal interval or two or more different intervals. For example, when the internal shape of the reaction vessel is rectangular, the heat transfer plates are arranged such that the heat transfer plate axes are parallel to each other between the heat transfer plates, and the heat transfer tube axes are parallel to each other between the heat transfer plates. Is provided. For example, when the inside of the reaction vessel is cylindrical, the heat transfer plate may be provided as described above, or the axis of the heat transfer plate is in the radial direction of the cross section of the reaction vessel. Between them, the axes of the heat transfer tubes may be provided so as to be parallel to each other (that is, radially).

The number of heat transfer plates accommodated in the reaction vessel is not particularly limited, and is practically determined from the amount of catalyst necessary for the reaction, and is usually several tens to several hundreds. Further, the number of heat transfer plates accommodated in the reaction vessel is such that the total capacity of the gaps between the heat transfer plates is 3 L (liters) or more from the viewpoint of realizing high productivity in industrial production of reaction products. The number is preferably 100L or more, and more preferably 250L or more. When the spacer is inserted in the gap between the heat transfer plates, the volume of one section surrounded by the spacer and the heat transfer plate is preferably 1L or more, and more preferably 10L or more.

The distance between the axes of the heat transfer plates accommodated in the reaction vessel is 10 to 50 mm from the viewpoint of sufficiently controlling the reaction temperature in the gas phase contact reaction. The axis of the heat transfer plate refers to the heat transfer plate in the cross section when the heat transfer plate is cut along the gas flow direction in the gap when the heat transfer plate is viewed from the gap. When all the heat transfer tubes are connected in a straight line on the plate, this straight line is said. When all the heat transfer tube connections are not in a straight line, between the two parallel lines sandwiching all the connection portions. A straight line passing through the midpoint.

The distance between the axes of the heat transfer plate effectively removes the heat associated with the reaction, prevents catalyst deterioration due to hot spots in the catalyst layer (in the case of exothermic reaction), while optimizing the temperature throughout the catalyst layer. The average value is 10 to 50 mm (1.1 to 5 times the sum of the half value of the width of heat transfer tubes in adjacent heat transfer plates) from the viewpoint of obtaining a high reaction rate and high reaction results by controlling the range. Is preferably 10 to 40 mm, more preferably 20 to 35 mm.

The distance between the axes of the heat transfer plate is affected by the diameter of the catalyst (usually preferably 1 to 10 mm for industrial catalysts), the reaction activity of the catalyst, and the high temperature resistance of the catalyst. For heat removal from the reaction heat, the smaller the distance between the axes of the heat transfer plate, the easier the control of the reaction. However, if the distance between the axes of the heat transfer plate is not less than 5-10 times the catalyst diameter, Bridging may occur during filling, and the filling density may be reduced.

The heat transfer plate may be arranged in the reaction container so that the convex edges of the surface of the heat transfer plate face each other, or the convex edge of the surface of one heat transfer plate is the surface of the other heat transfer plate. It may be arranged so as to face the concave edge of the surface.

The heat transfer tube is generally arranged in a direction in which the shaft of the heat transfer tube intersects the aeration direction in the reaction vessel when the heat transfer plate is accommodated in the reaction vessel. At this time, the angle between the axis of the heat transfer tube and the aeration direction in the reaction vessel is not particularly limited as long as the axis of the heat transfer tube intersects the gas aeration direction in the reaction vessel. In the heat transfer tube, the heat transfer tube axis is orthogonal to the aeration direction in the reaction vessel, that is, the flow direction of the heat medium flowing through the heat transfer tube is orthogonal to the aeration direction in the reaction vessel. It is more preferable from the viewpoint of controlling the reaction of the raw material by adjusting the temperature of the heat medium in the tube.

The heat transfer tube is formed of a material having heat transfer properties in which heat is exchanged between a heat medium in the heat transfer tube and a catalyst layer circumscribing the heat transfer tube. 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 cross-sectional shape of the heat transfer tube may be a circle, a substantially circular shape such as an elliptical shape or a rugby ball shape, a leaf shape formed by symmetrically connecting arcs, or a polygonal shape such as a rectangle. The shape which combined two or more of these may be sufficient. 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.

In each heat transfer plate, the diameter of the heat transfer tube in the axial direction of the heat transfer plate is (1) bending (flexure) rigidity in a direction orthogonal to both the axis of the heat transfer plate and the axis of the heat transfer tube, and (2) From the viewpoint of sufficiently ensuring the formability and accuracy of the shape of the heat tube, and (3) the heat transfer area necessary for removing reaction heat, and (4) the appropriate flow distribution of the reaction gas and the heat transfer coefficient of the catalyst layer. (5) From the viewpoint of obtaining an appropriate flow rate and heat transfer coefficient of the heat medium in the heat transfer tube, it is preferably 10 to 100 mm, more preferably 15 to 70 mm, and more preferably 20 to 50 mm. Further preferred.

In each heat transfer plate, the radius of the heat transfer tube in the direction perpendicular to the axis of the heat transfer plate is 1.5 mm to 25 mm from the viewpoint of sufficiently controlling the reaction temperature in the gas phase contact reaction. The radius of the heat transfer tube is as follows: (1) The distance between adjacent heat transfer plates is controlled in accordance with the reaction heat generated between the heat transfer plates, and the catalyst layer temperature is adjusted. (2) Reaction heat (4) Moderately ensuring the heat transfer area required for heat removal of (3) and (3) formability and accuracy of heat transfer tube shape, and (4) disordered flow velocity distribution of the reaction gas and heat transfer of the catalyst layer From the viewpoint of obtaining the coefficient, (5) pressure loss of the reaction gas, and (6) the flow rate and heat transfer coefficient of the heat medium in the heat transfer tube, it is preferably 1.5 to 25 mm, and preferably 3 to 20 mm. Is more preferably 5 to 15 mm.

In a plate reactor, the distance between the heat transfer plates is usually adjusted for the purpose of controlling the temperature of the catalyst layer. The respective radii of the heat transfer tubes in the axial direction of the heat transfer plate and in the direction perpendicular to the axis are also related to the distance between the heat transfer plates and the particle size of the catalyst. It is possible to achieve.

In addition, the shape and size of the cross section of each of the plurality of heat transfer tubes in one heat transfer plate may be constant or different.

The length of the heat transfer tube in the axial direction is not particularly limited, but is generally 0.5 to 20 m. The length of the heat transfer tube in the axial direction is preferably 3 to 15 m, more preferably 6 to 10 m, from the viewpoint of mass production of reaction products.

The length in the axial direction of the heat transfer plate (that is, the connecting direction of the heat transfer tube in the cross section of the heat transfer tube orthogonal to the axis of the heat transfer tube) is a viewpoint for preventing deformation such as bending of the heat transfer plate accommodated in the reaction vessel. Therefore, it is preferably 5 m or less, more preferably 0.5 to 2 m, and further preferably 0.5 to 1.5 m.

The plate width standard and availability of the steel plate used when manufacturing the heat transfer plate are also important for the production of a practical and inexpensive heat transfer plate. In particular, it is 1.5-2 m or less. Therefore, when it exceeds the plate width of the practical size, it is possible to join and use two or more steel plates, but the formability at the joining portion of the steel plates may be reduced.

In order to realize the design value of the distance between the surfaces of the heat transfer plate, errors caused when forming the steel plate are important. The errors caused when the steel sheet is formed include errors in the axial direction of the heat transfer tubes and errors in the connection direction of the heat transfer tubes, both of which are important. Particularly when the distance between the surfaces of the heat transfer plates is changed in the flow direction of the reaction gas (usually the connection direction of the heat transfer tubes), the forming accuracy of the shape of the heat transfer tube in the flow direction of the reaction gas is particularly important. From the viewpoint of suppressing these errors to a desired value or less, the length of the heat transfer plate in the axial direction is preferably 2 m or less.

The design value of the distance between the surfaces of the heat transfer plates facing each other is 5 to 50 mm. Here, the distance between the surfaces of the heat transfer plates refers to the distance between the surfaces of the heat transfer plates in the direction perpendicular to the surface that is equidistant from the surface of the heat transfer plate in the gap between the opposed heat transfer plates. Say distance. Or, the distance between the surfaces of the heat transfer plate is the cross section of the heat transfer plate when the heat transfer plate is cut along the gas flow direction in the gap when the heat transfer plate is viewed from the gap. The distance between the surfaces of the heat transfer plates in a direction perpendicular to a line that is equidistant from the axis of the heat transfer plate. In order to prevent leakage of the heat medium into the reaction vessel and leakage of gas from the reaction vessel to the heat transfer tube and the heat medium supply device when the heat transfer tube and the heat medium supply device are connected, the heat transfer tube is generally used. It is joined to the heat medium supply device by welding. Therefore, in general, the heat transfer plate is irreversibly fixed in the reaction vessel. For this reason, generally the arrangement | positioning of the heat-transfer plate in reaction container is predetermined by the design value according to the desired reaction result.

The design value can be determined based on the conditions of reaction control and reaction results. The conditions for controlling the reaction can be determined, for example, by the upper limit of the absolute value of the peak temperature of the catalyst layer during the reaction. The reaction results can be determined mainly by the yield of the product in consideration of, for example, the conversion rate of the raw material and the selectivity of the product. The design value of the catalyst layer when satisfying the reaction control conditions and satisfying the reaction performance conditions, considering further factors such as the type of catalyst, the composition and flow rate of the raw material gas, and the temperature of the heating medium. It is determined as the thickness, that is, the distance between the surfaces of the heat transfer plate. The peak temperature of the catalyst layer is the maximum temperature of the catalyst layer in the exothermic reaction and the minimum temperature of the catalyst layer in the endothermic reaction.

The design value is calculated by a computer simulation, an experiment by a test machine such as a plate type reactor having a simple configuration such as having only one pair of heat transfer plates and a small plate type reactor having a total capacity of about 3L. Alternatively, it can be obtained from an experiment using a tubular reaction tester having a single reaction tube filled with a catalyst and a jacket for circulating a heat medium around the reaction tube. The computer simulation can be performed using software such as CFX of Ansys Corporation, STAR-CD of CD adapco, and gPROMS of PSE.

The design value is preferably 5 to 50 mm from the viewpoint of precise control of the reaction, reaction results (reaction yield or selectivity), and productivity of the reaction product per catalyst amount (space time yield). It is more preferably 7 to 30 mm, and further preferably 10 to 25 mm. To achieve high catalyst productivity, the smaller the distance between the surfaces of the heat transfer plate, the easier the temperature control and the precise control of the reaction is possible, but the distance between the surfaces of the heat transfer plate is The particle size of the catalyst to be inserted is also limited. In the industrial catalyst, the particle size of the catalyst is often 1 to 10 mm, and the design value can be preferably determined within the above range from the viewpoint of these conditions.

The difference between the measured values with respect to the design value of the distance between the surfaces of the heat transfer plates facing each other (design value−measured value) is −0.6 to +2.0 mm. Here, “−” represents that the actual measurement value is smaller than the design value, and “+” represents that the actual measurement value is larger than the design value.

The distance between the surfaces of the heat transfer plates may be a distance between any positions on the surfaces of the opposing heat transfer plates as long as the distance is within a range of 5 to 50 mm. For example, the distance between the surfaces of the heat transfer plates is opposite when the heat transfer tube located on the most upstream side in the direction of flow of the raw material gas in the reaction vessel is the heat transfer tube A among the heat transfer tubes included in the heat transfer plate. The distance between the convex edges of the heat transfer tubes A in the pair of heat transfer plates may be, or the concave edge by the connection portion between the heat transfer tubes A in the pair of opposed heat transfer plates and the heat transfer tubes adjacent to the downstream side thereof. May be a distance between the concave edge and the other or one of the connection portions of the heat transfer tube A and the heat transfer tube adjacent to the downstream side of one or the other heat transfer plate of the pair of opposed heat transfer plates. The distance between the heat transfer plate and the convex edge by the heat transfer tube A may be used.

The distance between the surfaces of the heat transfer plate can be measured, for example, by inserting a rod having the same thickness as the design value of the distance between the surfaces. Further, the distance between the surfaces of the heat transfer plate is, for example, the length of the design value that is arranged perpendicular to the axis of the insertion rod member at the tip of the insertion rod member and the insertion rod member inserted into the gap. A measuring member having a measuring rod member is inserted into the gap, and the angle and rotation angle of the shaft of the inserting rod member when the end of the measuring rod member contacts the surface of the heat transfer plate in the gap are measured. By doing this, the distance between the surfaces of the heat transfer plate at the portion in contact with the measuring rod member can be obtained from this angle.

If the difference between the measured value and the design value is larger than +2.0 mm, the reaction cannot be sufficiently controlled, the runaway reaction can be suppressed, the catalyst can be prevented from deteriorating, and the reaction yield cannot be reduced. is there. Further, if the difference between the measured value and the design value is less than −0.6 mm, the catalyst feed to the gap between the heat transfer plates may be hindered, or the catalyst feed may be performed without any trouble. In some cases, however, the packing density of the formed catalyst layer is lowered, the catalyst amount is insufficient, and the desired reaction rate may not be achieved. The difference between the measured value and the design value is preferably −0.5 to +1.5 mm, more preferably −0.5 to +1.0 mm, from the viewpoint of more precise reaction control. More preferably, it is −0.3 to +1.0 mm.

The difference between the measured value and the design value is most preferably in the range of −0.6 to +2.0 mm in the whole plate reactor, but it prevents the runaway reaction and maintains high productivity. From the viewpoint of achieving both, it is preferable that a difference from the design value of 50% or more of all measured values is included in −0.6 to +2.0 mm, and 70% or more of all measured values are included. It is more preferable that the difference with respect to the design value is included in −0.6 to +2.0 mm, and a difference with respect to the design value of 80% or more is included in −0.6 to +2.0 mm. More preferably, a difference from the design value of 90% or more is included in −0.6 to +2.0 mm.

The measurement point of the actually measured value is preferably 2 to 30, more preferably 5 to 25, and further preferably 10 to 20 in the axial direction of the heat transfer plate. The measurement point of the actual measurement value is preferably 2 to 50, more preferably 5 to 30, and further preferably 10 to 20 in the axial direction of the heat transfer tube in the heat transfer plate.

As will be described later, in order to control the interval between adjacent heat transfer plates, a spacer (partition) may be inserted between the heat transfer plates, but in that case, the spacer has the effect of adjusting the interval between the heat transfer plates. Therefore, in this case, the measured value may be measured at two locations from the center position between the spacers. The installation interval when installing multiple spacers is usually 50 cm to 1 m. However, a heat transfer plate that uses a highly rigid heat transfer plate and devise side plates and welds that join the heat transfer plates together can be used. If the distance between them can be controlled, the distance between the spacers can be set to 1 m or more.

For example, when the heat transfer plate is formed by joining two formed steel plates, the difference between the measured values and the design values is sufficiently small (for example, the error is ± 0). -0.6 to +2 by performing a method of selecting and using a shaped steel plate with high accuracy, and a method of selecting and correcting a shaped steel plate with insufficient accuracy to improve accuracy. 0.0 mm. For errors with respect to the design value of the steel sheet forming, for example, by installing a laser displacement meter on both sides of the formed steel sheet, by moving the displacement meter or the steel sheet, measuring the displacement of both sides of the formed steel sheet, The molding accuracy and the error with respect to the design value can be obtained.

Furthermore, using a heat transfer tube having a length of 10 m or less in the axial direction of the heat transfer tube as the heat transfer tube is effective from the viewpoint of preventing the heat transfer tube and the heat transfer plate from being bent, and the actual measurement with respect to the design value is performed. This is preferable from the viewpoint of setting the difference in value between -0.6 and +2.0 mm.

The difference between the measured values with respect to the design value may be a single value, but depending on the expected reaction rate when used in the gas phase catalytic reaction, a plurality of different in the axial direction of the heat transfer plate It may be a value. For example, in the gas-phase contact reaction, the difference between the measured values with respect to the design value at the inlet of the raw material gas in the gap between the heat transfer plates where the reaction is particularly intense and the reaction rate of the raw material is low is performed. From the viewpoint of suppressing reaction runaway, making it smaller than that at the outlet, that is, the difference between the measured values with respect to the design value is smaller on the upstream side in the ventilation direction in the gap between the heat transfer plates. preferable.

From this point of view, it is preferable to reduce the difference between the measured values with respect to the design value at a position where the reaction rate of the raw material is 70% or less, and the design value at a position where the reaction rate of the raw material is 60% or less. It is more preferable to make the difference between the measured values with respect to the value smaller, and it is more preferable to make the difference between the measured values with respect to the design value at a position where the reaction rate of the raw material is 50% or less. Further, from the above viewpoint, it is preferable that the difference of the actual measurement value with respect to the design value at the position is smaller by 0.2 mm or more in absolute value than the difference of the actual measurement value with respect to the design value at another position. More preferably, the absolute value is 0.5 mm or smaller.

In the gap between the heat transfer plates, the position where the reaction rate of the raw material has a predetermined value in the axial direction of the heat transfer plate is the cross-sectional shape and size of the heat transfer tube, the temperature of the heat medium flowing through the heat transfer tube, and The flow rate, the distance between the surfaces of the heat transfer plate, the type of catalyst, the composition of the raw material gas and its flow rate, etc. are determined by various conditions relating to the progress of the reaction and the heat transfer. It can be determined from calculation by computer simulation.

The heat medium supply device is a device for joining a heat transfer tube at both ends of the heat transfer tube in the heat transfer plate and supplying a heat medium having a desired temperature to the heat transfer tube. As the heat medium supply device, a normal device for supplying a heat medium to the heat transfer tube in the plate reactor can be used. The heat medium supply device may be a device that supplies the heat medium in one direction to all of the plurality of heat transfer tubes, or supplies the heat medium in one direction to a part of the plurality of heat transfer tubes, and the plurality of heat transfer tubes The other part may be a device for supplying a heat medium in the reverse direction.

Further, the heat medium supply device has a plurality of heat medium circulation chambers that are partitioned in a direction transverse to the axial direction of the heat transfer plate, so that a plurality of reaction zones are provided in the catalyst layer along the axial direction of the heat transfer plate. It is preferable from the viewpoint of formation. Moreover, it is preferable that a heat-medium supply apparatus is an apparatus which circulates a heat medium inside and outside a reaction container via the said heat exchanger tube.

Furthermore, the heat medium supply device has a device for adjusting the temperature of the heat medium supplied to the heat transfer tube. As such an apparatus, for example, a heat exchanger provided in a circulation path of the heat medium, and a heat medium mixing apparatus for mixing the heat medium of different temperatures with the heat medium in the chamber in the heat medium supply apparatus , A heat medium temperature measuring device, and a device for adjusting the flow rate of the heat medium. The heat medium mixing device includes, for example, a distribution pipe that protrudes into the heat medium supply device and can distribute and supply the heat medium in the heat medium supply device, a liquid passing plate provided in the heat medium supply device, and A static mixer called a so-called static mixer can be used.

Examples of the distribution pipe include a distribution pipe having a plurality of liquid passage openings such as slits and holes in the pipe wall along the longitudinal direction of the distribution pipe, and a distribution pipe further including a branch pipe having the liquid passage opening. . The distribution pipe is preferably provided so as to extend in a direction orthogonal to the flow direction of the heat medium in the heat medium supply device, and the distribution pipe having a branch pipe includes a main pipe and a branch pipe, Are provided so as to extend in a direction perpendicular to the flow direction of the heat medium in the heat medium supply device, and the extension directions of the main pipe and the branch pipe are perpendicular to each other. It is preferable from the viewpoint of improving the efficiency in dispersion of the medium and suppressing pressure loss.

The first plate reactor may further include other components other than those described above. Examples of such other components include a spacer, a vent plug, a temperature measuring device, and a plate clamping unit.

The spacer (partition) is a member for forming a predetermined interval between the heat transfer plates. It is preferable that the spacer is in contact with the surface of the heat transfer plate and has sufficient rigidity to maintain the space between the heat transfer plates. The spacer is a member that intermittently contacts the surface of the heat transfer plate in the axial direction of the heat transfer plate, so that when the spacer is formed of steel, the amount of steel required for the plate reactor is reduced. It is preferable from the viewpoint. In addition, the spacer is preferably a member that continuously contacts the surface of the heat transfer plate in the axial direction of the heat transfer plate from the viewpoint of preventing deformation of the heat transfer plate in the reaction vessel. Furthermore, the spacer is a member that does not allow the passage of the catalyst in the axial direction of the heat transfer tube. From the viewpoint of filling the catalyst, the gap between the heat transfer plates can be partitioned into compartments of a predetermined capacity. This is preferable from the viewpoint of easily and accurately filling the gaps between the heat plates with the catalyst. It is preferable from the viewpoint of preventing deformation of the heat transfer plate in the reaction vessel that the spacers are arranged at 10 or more locations in the axial direction of the heat transfer tube or at intervals of 100 to 1,000 mm. Examples of the spacer include members in various forms such as a bar, a plate, and a block, and a partition in a second plate reactor described later.

The vent plug has air permeability, and in the case of further having a gap of the heat transfer plate or a spacer, the end of the section in the axial direction of the heat transfer plate is detachable so as not to allow passage of the catalyst. It is a member for closing. As such a vent plug, for example, a vent plate that closes a gap between the heat transfer plates in the axial direction of the heat transfer plate or an end of the partition, and the vent plate is provided with the heat transfer plate or the spacer. Examples thereof include a member having a locking member that is detachably locked. The vent plug is preferably a member that is detachably disposed at the end of the compartment from the viewpoint of easily and accurately filling the gap between the heat transfer plates. As the vent plug, a vent plug in a second plate reactor described later can be used.

The temperature measuring device is a device that measures the temperature of the catalyst layer formed in the gap between the heat transfer plates. Examples of such a temperature measuring device include a device having a flexible support and a temperature measurement unit supported by the support. As the support, a flexible string, band, chain, or tube can be used. Examples of the temperature measuring unit include a platinum resistance temperature detector, a thermistor, a thermocouple, and an optical fiber type temperature measuring device.

The number of the temperature measuring devices installed per reaction vessel is preferably 2 to 20 from the viewpoint of grasping the temperature of the catalyst layer. The thickness (width) of the support is preferably 0.5 to 5 mm. Further, the temperature measuring unit is preferably provided on one support from 1 to 30 from the viewpoint of reflecting the measurement of the temperature of the catalyst layer in the control of the reaction, and in the case where a plurality of reaction zones are formed in the catalyst layer. 1 to 10 are preferably provided for one reaction zone. In the gap between the heat transfer plates, the temperature measuring device stretches the support in a straight line at a position equidistant from the adjacent heat transfer plates, and the catalyst is placed in the gap while the support is stretched. By filling, it can arrange | position appropriately in the said clearance gap. For the purpose of checking the influence of deformation of the heat transfer plate, partial reaction abnormality due to the shape error of the heat transfer rod and temperature distribution abnormality of the catalyst layer, the temperature measurement position may be two or more in one catalyst layer. is necessary. From the viewpoint of ease of reaction control, it is preferable that there are many temperature measurement positions.

The plate clamping portion is in contact with the heat transfer plates at both ends in the direction in which the heat transfer plates are arranged so as to block the flow of the raw material gas at least along the axial direction of the heat transfer tubes, and the plurality of heat transfer plates It is a member that is sandwiched in the direction in which the heat transfer plates are arranged. The plate clamping part may be provided in the reaction container or may constitute a pair of opposing walls of the reaction container. The plate clamping portion is preferable from the viewpoint of preventing formation of a gas retention portion on the wall of the reaction vessel. As such a plate clamping portion, a pair of clamping plates that abut the entire heat transfer tube in the extending direction of the heat transfer tube on at least one heat transfer tube of the heat transfer plates at both ends in the direction in which the plurality of heat transfer plates are arranged. And a holding rod for penetrating and holding these clamping plates.

Further, the heat transfer plate for holding the holding bar is a member that can connect the holding plate in the opposing direction at a predetermined interval, such as a bar having a screw to which a nut can be screwed at least at the tip. More preferable from the viewpoint of finely adjusting the interval with the catalyst, from the viewpoint of easily installing a scaffold during the filling of the catalyst and the inside of the plate reactor, and from the viewpoint of being divertable to a plate reactor under other conditions .

In the first plate reactor, when this plate reactor is used for a gas phase catalytic reaction, a catalyst is filled in a gap between the heat transfer plates. The said catalyst is selected according to the raw material and reaction product of a gaseous-phase contact reaction. As the catalyst, a normal granular catalyst filled in a gap between a tube or a heat transfer plate by a gas phase contact reaction can be used. One or more catalysts may be used. An example of such a catalyst is a catalyst having a particle size (longest diameter) of 1 to 20 mm. The particle size of the catalyst used is more preferably 1 to 10 mm. Moreover, as a shape of a catalyst, a well-known thing can be used, for example, spherical shape, cylindrical shape, Raschig ring shape, and saddle shape are mentioned.

<First production method of reaction product>
The first plate reactor has a heat exchange capability, and among the gas phase catalytic reactions in which a raw material gas and a solid catalyst are used, an exothermic reaction or an endothermic reaction that requires a heat exchange function in the reactor. Can be used. That is, the first plate type reactor supplies a gaseous raw material to the reaction vessel and passes it through the catalyst layer, and supplies a heat medium having a predetermined temperature to a plurality of heat transfer tubes constituting the heat transfer plate. And a first reaction method for producing a reaction product that reacts a raw material gas in the presence of the catalyst to produce a gaseous reaction product. Such a production method can be performed in the same manner as the gas phase catalytic reaction using a known plate reactor, or can be performed under the same conditions as the gas phase catalytic reaction using a known multitubular reactor. .

Examples of the gas phase catalytic reaction accompanied by the exothermic reaction include: a reaction that produces propane, propylene and oxygen or one or both of acrolein and acrylic acid; and one or both of methacrolein and methacrylic acid produced from isobutylene and oxygen. Reaction; reaction for producing ethylene oxide from ethylene and oxygen; reaction for producing one or both of unsaturated aliphatic aldehyde and unsaturated fatty acid having 3 carbon atoms from hydrocarbon having 3 carbon atoms and oxygen; carbonization having 4 carbon atoms Reaction to produce one or both of unsaturated aliphatic aldehyde having 4 carbon atoms and unsaturated fatty acid from oxygen and / or hydrogen and Tascherbutanol and oxygen; carbon from unsaturated aliphatic aldehyde having 3 or 4 carbon atoms and oxygen Reactions that produce unsaturated fatty acids of

number

3 or 4; hydrocarbons having 4 or more carbon atoms such as n-butane and benzene and oxygen And the like; reaction producing butadiene by oxidative dehydrogenation of butene; reaction of producing phthalic acid from xylene and / or naphthalene with oxygen; reaction produces Luo maleic acid.

Examples of the gas phase contact reaction accompanied by the endothermic reaction include a reaction of generating styrene by dehydrogenation of ethylbenzene.

The first production method of the reaction product is preferably used for the production of one or both of metaacrolein and methacrylic acid, one or both of acrolein and acrylic acid, maleic acid, phthalic acid, ethylene oxide, or butadiene. it can.

For example, the first production method of the reaction product for producing one or both of (meth) acrolein (acrolein or methacrolein) and (meth) acrylic acid is that the first plate reactor is used as the reactor. , Propane, propylene or isobutylene as described in Japanese Patent Application Laid-Open No. 2003-252807 can be performed by a known method of oxidizing molecular oxygen or a gas containing the same in the presence of a catalyst. it can. The catalyst includes a Mo—V—Te composite oxide catalyst, a Mo—V—Sb composite oxide catalyst, a Mo—Bi composite oxide catalyst, and Mo— A well-known catalyst can be used by a well-known usage in the use in the gas phase catalytic oxidation reaction which produces | generates (meth) acrylic acid, such as a V type complex oxide catalyst.

Further, the first production method of the reaction product can be suitably used in a gas phase contact reaction involving an exothermic reaction as a reaction of the raw material in the raw material gas in the presence of the catalyst.

In the first production method of the reaction product, the peak temperature in the temperature distribution in the axial direction of the heat transfer plate of the catalyst layer during the reaction is the peak temperature of the catalyst layer set during the design of the first plate reactor. A heat medium having a set temperature is supplied from the heat medium supply device to the heat transfer tube. Such temperature control of the heat medium can be performed using a known control method such as feedback control based on the design value. The temperature of the heat medium during the reaction is preferably controlled so that the peak temperature of the catalyst layer is ± 20 ° C. with respect to the designed value, and the peak temperature of the catalyst layer is ± 10 with respect to the designed value. More preferably, the reaction is carried out so that the peak temperature of the catalyst layer becomes ± 5 ° C. with respect to the design value. The set value is obtained from an experiment in determining the design value of the plate reactor, or determined in the calculation by the computer simulation. The temperature of the heat medium can be controlled using the heat medium supply device.

<Production method of first plate reactor>
In the first plate reactor, the heat transfer plate is disposed at an interval where the distance between the surfaces of the opposed heat transfer plates is the design value, and the heat transfer tube and the heat medium supply device are welded or the like. Obtained by bonding. The heat transfer plates can be arranged at intervals corresponding to the design values, for example, by arranging the heat transfer plates via bar members having a thickness equal to the design value. The rod member is extracted from the gap between the heat transfer plates after joining the heat transfer tube and the heat medium supply device.

Alternatively, when the plate-type reactor has the spacer, the heat transfer plate may be arranged at an interval corresponding to the design value by alternately and densely arranging the heat transfer plate and the spacer before joining. it can.

Hereinafter, embodiments of the present invention will be described more specifically with reference to the drawings.

<First embodiment>
The first plate reactor has a heat transfer tube 1 as shown in FIGS. 1 to 4, for example, and a plurality of heat transfer plates 2 provided side by side in the reaction vessel, and the heat transfer plates 2 are arranged side by side. A pair of sandwiching plates 3 that are in contact with the heat transfer plates 2 at both ends in the direction at least along the axis of the heat transfer tube 1 and sandwich the plurality of heat transfer plates 2 in the direction in which the heat transfer plates 2 are arranged, and sandwiching these A plurality of holding rods 4 that connect the plates 3, a heat medium supply device 5 that abuts against both ends of the heat transfer tube 1 in the heat transfer plate 2 and supplies a heat medium to the heat transfer tube 1, and a shaft of the heat transfer tube 1. In the direction, the gas distribution part 6 that covers both ends of the plurality of heat transfer plates 2 and distributes the gas to the gap between the adjacent heat transfer plates 2 and the gap between the adjacent heat transfer plates 2 in the gas ventilation direction Along multiple compartments containing the packed catalyst A partition 7 for cutting, a vent plug 8 for closing the lower end of each section, a temperature measuring device 9 stretched in a direction crossing the axis of the heat transfer tube 1 at the center of the predetermined section, and a plurality of heat transfer plates 2 and a perforated plate 10 provided so as to cover the upper side of 2.

The heat transfer tube 1 has, for example, a diameter (long axis, L) in the axial direction of the heat transfer plate 2 of 30 to 50 mm, and a diameter (short axis, H) in the direction orthogonal to the axial direction of the heat transfer plate 2 is 10 to 20 mm. The cross-sectional shape is a tube whose main component is a circular arc, an elliptical arc, a rectangle, and a part of a polygon. The length of the heat transfer tube 1 is usually 0.1 to 20 m, for example 10 m. FIG. 5 shows a heat transfer tube having a leaf shape in cross section with an arc as a component of the cross section. In FIG. 5, the major axis of the heat transfer tube is represented by L, and the minor axis is represented by H.

The heat transfer plate 2 has a shape in which a plurality of heat transfer tubes 1 are connected by an edge having a cross-sectional shape. The heat transfer plate 2 is formed by joining two steel plates formed so as to form an elliptical arc continuously by welding with convex edges formed at the ends of the arcs of both steel plates. As the steel plate, a steel plate having a thickness of 2 mm or less, preferably 1 mm or less is used. The shape of the formed steel plate is precisely inspected. For example, a formed steel plate having an error with respect to the design value of forming within ± 1% is used as it is, and the forming with an error with respect to the design value of forming exceeds ± 5%. The steel sheet thus used is used after being corrected so that the error with respect to the design value of forming is within ± 2%.

Adjacent heat transfer plates 2 may be arranged in parallel so that the convex edges of the surfaces face each other, but in the plate reactor of FIG. 1, the convex edges of the surface of one heat transfer plate 2 and The other heat transfer plate 2 is arranged in parallel so as to face the concave edge on the surface.

The heat transfer plate 2 may be composed of the same heat transfer tube 1 or may be composed of the heat transfer tubes 1 having different cross-sectional sizes. For example, in the heat transfer plate 2, the upper portion, the middle portion, and the lower portion of the heat transfer plate 2 may be configured by three types of heat transfer tubes having different cross-sectional sizes. More specifically, as shown in FIG. 7, the heat transfer plate 2 is formed so that the major axes of the three types of heat transfer tubes are arranged in a straight line. 20% of the height of the heat transfer plate 2 is composed of the heat transfer tube a having the largest cross section, and the middle part of the heat transfer plate 2 is the second cross section of 30% of the height of the heat transfer plate 2 The lower part of the heat transfer plate 2 is constituted by the heat transfer tube c having the smallest cross-sectional area for 40% of the height of the heat transfer plate 2, and the heat transfer plate 2. 10% of the height of the heat transfer plate 2 may be formed by the joining plate portions at the upper end portion and the lower end portion of the heat transfer plate 2. The cross-sectional shape of the heat transfer tube a is, for example, a long diameter (L) of 50 mm and the short diameter (H) is a leaf shape of 20 mm, and the cross-sectional shape of the heat transfer tube b is, for example, a long diameter (L) of 40 mm and short. The diameter (H) is a leaf shape of 16 mm, and the cross-sectional shape of the heat transfer tube c is, for example, a leaf shape having a major axis (L) of 30 mm and a minor axis (H) of 10 mm.

The length of the heat transfer plate 2 in the axial direction of the heat transfer plate 2 is usually 0.5 to 10 m, preferably 2 m or less. When the length of the heat transfer plate 2 in the axial direction is 2 m or more, the two heat transfer plates 2 can be joined or combined.

As shown in FIGS. 2 and 3, the sandwiching plate 3 is a pair of plates, for example, a pair of stainless steel plates. The clamping plate 3 is formed larger than the heat transfer plate 2 so that it can be joined by the holding rod 4 at the edge.

As shown in FIG. 3, the holding rod 4 is a plurality of rods that penetrate and connect the pair of clamping plates 3, and is, for example, a stainless rod having screws at both ends. As shown in FIGS. 2 to 4, the sandwiching plate 3 is fixed by nuts at both ends of the holding rod 4 at positions where it comes into contact with the outer periphery of the heat transfer tube 1 (the heat transfer tube a) above the heat transfer plate 2. The The clamping plate 3 can be fixed by changing the position in the direction of clamping the heat transfer plate 2 within the range of the installation length of the screws of the holding rod 4. Further, the holding bar 4 is arranged at a position overlapping the partition 7 arranged in the gap between the heat transfer plates 2 in the vertical direction. A pair of clamping plates 3 and holding rods 4 constitute the plate clamping portion.

As shown in FIGS. 1 and 2, the heat medium supply device 5 is a pair of containers that are in contact with both ends of the heat transfer tube 1 of the heat transfer plate 2. A pair of

jackets

11, 12, a nozzle 13 provided in the jacket and used for supplying and discharging the heat medium; a heat exchanger 14 for adjusting the temperature of the heat medium discharged from the jacket 11; And a pump 15 for circulating a heat medium to and from the heat exchanger 14. The heating medium supply device 5 is airtightly joined to the sandwiching plate 3 at the side edge portion of the sandwiching plate 3 using a normal fixing member such as a screw and a nut and a seal such as a gasket.

The inside of the

jackets

11 and 12 traverses the axis of the heat transfer plate 2 so that the heat medium flows in one direction or the opposite direction in each predetermined number of heat transfer tubes 1 and the heat medium reciprocates between the

jackets

11 and 12. It may be appropriately divided so as to communicate with or cut off along the direction to perform.

Note that the heat medium supply device 5 may be a device that causes the heat medium to flow in one direction in all the heat transfer tubes 1 from one jacket 11 to the other jacket 12, as indicated by an arrow Y in FIG. Good.

Furthermore, the heat medium supply device 5 is, for example, a heat medium mixed in the

jackets

11 and 12 or in any one of the plurality of chambers in the

jackets

11 and 12 that are blocked with respect to the axial direction of the heat transfer plate 2. I have a device. As shown in FIG. 6, the heat medium mixing device includes a nozzle 16 that communicates with the inside and outside of the jacket, and a nozzle 16 that is connected to the inside of the jacket and extends in a direction perpendicular to the flow direction of the heat medium within the jacket. And a pipe 17. The distribution pipe 17 is, for example, a pipe having a closed end and a plurality of holes provided over the entire length of the distribution pipe.

The gas distribution unit 6 includes, for example, a reaction vessel cover that forms a cover that is separated from the end portions of the plurality of heat transfer plates, and that seals both ends of the side wall of the reaction vessel formed by the heat medium supply device and the plate holding unit. In addition, a gas vent (nozzle 18) through which a source gas is supplied or a reaction product gas is discharged can be used. As the reaction vessel cover, covers having various shapes such as a dome shape, a conical shape, a quadrangular shape, a triangular prism shape, and a housing can be used. Moreover, the said vent hole can use the normal vent hole which has the nozzle opened to a reaction container cover, and the flange formed in the edge part, for example. The reaction vessel cover is usually provided in a pair with respect to the side wall of the reaction vessel, and these may be the same or different. In addition, one vent is usually provided in the reaction vessel cover, but a plurality of vents may be provided. Further, a pair of the vents are usually provided in the plate reactor, but these may be the same or different.

More specifically, as shown in FIGS. 1 and 3, the gas distribution unit 6 includes an upper end edge of the sandwiching plate 3 and an upper end edge of the

jackets

11 and 12, and a lower end edge of the sandwiching plate 3 and the

jackets

11 and 12. A pair of members that cover both ends of the plurality of heat transfer plates 2 are hermetically joined to the lower end edges, for example, using the fixing member and a seal. The gas distribution unit 6 is, for example, a kamaboko type stainless steel lid. Each of the gas distribution units 6 includes a nozzle 18 and a manhole 19. The gas is supplied to the gap between the heat transfer plates 2 through the nozzle 18 of one gas distribution unit 6, and the gas is discharged from the gap through the nozzle 18 of the other lid. In the plate reactor, a reaction vessel is formed by airtightly joining the sandwich plate 3, the heating medium supply device 5, and the gas distribution unit 6.

The manhole 19 is an open / close door for an operator to enter and exit the gas distribution unit 6 in a state where the gas distribution unit 6 is installed. The arrangement of the nozzle 18 and the manhole 19 is not particularly limited, but when the gas distribution unit 6 is a kamaboko type lid, for example, as shown in FIG. 1, the nozzle 18 is provided at one end of the lid, and the manhole 19 is a lid. Provided at the other end. Further, the gas distribution unit 6 includes a safety device (not shown) such as a safety valve or a rupture disc as a safety measure in the case of an abnormal sudden rise in pressure or abnormal reaction, and the main body of the gas distribution unit 6 at the inlet and / or outlet. Or the nozzle 18. The gas outlet 6 and the manhole 19 on the outlet side of the reactor, in the case where decomposition of the target product and accumulation of by-products generated by the retention of the gas containing the reaction product occur, It is desirable to install structures and additions to reduce

The partition 7 is provided between the adjacent heat transfer plates 2 along the direction crossing the axis of the heat transfer tube 1, that is, the gas flow direction in the plate reactor. As shown in FIG. 7, the partition 7 is a plate-like member with sufficient rigidity that comes into contact with the surface of the heat transfer tube 1, for example, and has a window 20 that is a rectangular through-hole at the bottom. The partition 7 is a spacer that maintains the interval between the heat transfer plates 2 at a predetermined interval. The partitions 7 may be provided at the same interval in the whole plate reactor or may be provided at different intervals. The partitions 7 are provided in parallel at the same interval of 400 mm, for example, and form a plurality of compartments having a volume of 12 L in the gaps between the heat transfer plates 2.

As shown in FIG. 8, the vent plug 8 has a rectangular vent plate 21 having the same cross-sectional shape as each section, a first skirt portion 22 provided downward from the short side of the vent plate 21, and the vent plate 21. And a second skirt portion 23 that hangs downward from the long side. The first skirt portion 22 is formed with a rectangular locking window 24 and a locking claw 25 provided adjacent thereto.

The ventilation plate 21 is, for example, a plate in which circular holes of 2 mm are formed with an opening rate of 30%. The locking window 24 is formed in a size having a width and a height for accommodating the locking claw 25. The locking claw 25 is formed by bending two parallel cuts from the lower edge of the first skirt portion 22 so as to protrude outward. In the pair of first skirt portions 22 facing each other, one locking window 24 and the other locking claw 25 face each other, and one locking claw 25 and the other locking window 24 face each other. The window 20 of the partition 7 is formed in a size having a width and a height that include the locking window 24 and the locking claw 25 at the same time.

The vent plug 8 is inserted into each section from the lower end of each section with the ventilation plate 21 up. At this time, the latching claw 25 is pressed against the partition 7 against the outward bias, but when it reaches the window 20, it is released from the pressing of the partition 7 as shown in FIG. Advancing toward and locking to the window 20.

As shown in FIG. 2, for example, the temperature measuring device 9 is provided in an outermost gap and an arbitrary gap inside the gap among a plurality of gaps formed by the heat transfer plate 2. Further, the temperature measuring device 9 is provided at a plurality of locations including the vicinity of the inlet and the outlet of the heat medium along the axial direction of the heat transfer tube 1, that is, the flow direction of the heat medium, in one gap between the heat transfer plates 2. Provided. The installation position of the temperature measuring device 9 can be determined according to the temperature difference between the upstream heat medium and the downstream heat medium in one heat transfer tube 1 of the heat transfer plate 2. For example, in the case where the temperature of the heat medium is controlled in units of 0.5 ° C., the temperature measuring device 9 has a temperature difference between the upstream heat medium and the downstream heat medium in one heat transfer tube 1 of the heat transfer plate 2. Is provided at a position of 2 ° C. or higher.

As shown in FIG. 10, the temperature measuring device 9 includes a flexible support 26, a plurality of temperature measuring units 27 supported by the support 26, and a horizontal direction extending from the support 26. A plurality of spacer rods 28 in contact with the surface of the heat plate 2, a flange 29 provided at the base end of the support 26, a connector 30 connected to the flange 29, a cable 31 connected to the connector 30, and the support 26 And a fixing flange 32 provided at the front end of the head.

The support 26 is a stainless steel tube having an average wall thickness of 0.2 mm. Eleven thermocouples that are temperature measuring units 27 are inserted in the support 26. Each temperature measurement part 27 is arrange | positioned according to the temperature change in each catalyst layer. For example, the temperature measuring unit 27 is provided in the vicinity of the inlet of the reaction gas in the catalyst layer, in the vicinity of the outlet, and at three locations where the maximum temperature is predicted in each reaction zone of each catalyst layer. More specifically, as shown in FIG. 10, the temperature measuring unit 27 has a central portion of the first reaction zone formed by the heat transfer tube a group, one at the upper end of each gap in the ventilation direction of each gap. Three at the center of the second reaction zone formed by the heat transfer tube b group, three at the top of the third reaction zone formed by the heat transfer tube c, and one at the lower end of each gap. , Respectively.

In addition, the position where the temperature difference of the heat medium in each heat transfer tube 1 is 2 ° C. or more and the position where the maximum temperature is predicted in each reaction zone of each catalyst layer are the results of experiments using this reactor tester. Or based on the result of computer simulation using software such as CFX of Ansys Corporation, STAR-CD of CD adapco, or gPROMS of PSE.

The spacer rod 28 is a stainless steel rod whose base end is fixed to the support 26 and extends in the horizontal direction. The spacer rod 28 has a length corresponding to the position on the support 26, and the tip of the spacer rod 28 contacts the surface of the heat transfer plate 2 when the support 26 is supported by the center surface of each gap. Have a length to Three spacer rods 28 are provided from the center portion to the base end portion of the support 26, and are provided so as to alternately contact each of the opposing heat transfer plates 2.

The flange 29 is placed on, for example, a flange support member that supports the flange 29 at a predetermined height in the reaction vessel in order to fix the support 26 to the upper portion of the reaction vessel. The flange support member is, for example, a member that is inserted with a bolt suspended from the upper gas distributor 6 and is maintained at a predetermined height by a nut. For example, two steel wires sandwiching the support 26 and a bolt A steel wire support member that supports two steel wires and a nut that tightens the steel wire support member in which the bolt is inserted into the bolt hole from below. The fixing flange 32 is a disk or a ring having a diameter larger than the diameter of the hole in the vent plate 21 of the vent plug 8. For example, after the tip of the support 26 is passed through the hole of the vent plate 21, Fixed to the tip.

The temperature measuring device 9 shown in FIG. 10 has the tip of the support 26 fixed to the vent plug 8 by the fixing flange 32 at a position equidistant from each heat transfer plate 2 at the lower end of the gap in the vertical direction. At the upper end of the gap, the base end of the support 26 is fixed by the flange support member at a position equidistant from each heat transfer plate 2. By tightening the nut of the flange support member, the nut moves upward, the support body 26 is stretched upward by the flange support member, and each spacer rod 28 is in a straight line with the surface of the heat transfer plate 2 being in contact with it. Become.

In the plate reactor, due to the above-described configuration, the heat transfer plates 2 are arranged in parallel at equal intervals, for example, the shortest distance between the outer walls of the heat transfer tubes a is 14 mm (the distance between the axes of the heat transfer plates 2 is 30 mm). is doing.

The heat transfer plate 2 is arranged at a desired position by alternately arranging the heat transfer plates 2 and the spacers 7, and both ends of the heat transfer tube 1 are welded and joined to the

jackets

10 and 11 at this position. Here, the distance between the surfaces of the heat transfer plate 2 is the gas flow direction (BB in FIG. 1) when the heat transfer plate 2 is viewed from the gap between the heat transfer plates 2 (FIG. 1). The heat transfer plate in a direction perpendicular to the line that is equidistant from the axis of the heat transfer plate 2 in the cross section (FIGS. 3 and 5) of the heat transfer plate 2 when the heat transfer plate 2 is cut along the line ' The distance between the two surfaces. Since the heat transfer plate 2 is arranged so that the axis of the heat transfer plate 2 is along the vertical direction and the axis of the heat transfer tube 1 is along the horizontal direction, for example, between the surfaces of the heat transfer plate 2 The design value of the distance is that in the heat transfer plate 2 arranged so that the axis is in the vertical direction, the distance between the surfaces of the heat transfer plate 2 in the horizontal direction and the convex edge of one heat transfer plate and the other When the distance between the concave edges of the heat transfer plate is 20 mm, and the measured value of the distance is 19.5 to 21 mm, the difference between the distances between the surfaces of the heat transfer plate 2 at this time is −0. 5 to 1.0 mm.

Each section of the gap between adjacent heat transfer plates 2 is filled with a catalyst. As the catalyst, for example, a molybdenum (Mo) -bismuth (Bi) catalyst having a maximum average particle diameter of 5 mm and a ring shape is used. A compartment formed by the heat transfer plate 2 and the partition 7 is filled with a catalyst having a predetermined volume corresponding to the volume of the compartment.

FIG. 11 shows a state in which the gap between the heat transfer plates 2 is filled with the catalyst. As shown in FIG. 11, the heat transfer plate 2 has two thin plates formed into a circular arc, an elliptical arc, a rectangle or a part of a polygon, joined to face each other, and flow paths for three kinds of heat media having different cross-sectional areas. 33, 34, and 35 are formed. The width of the flow path 33 is the largest, and therefore the width of the catalyst layer 36 is the narrowest between the flow paths 33. The widths of the

flow paths

34 and 35 are sequentially smaller than that of the flow path 33, and therefore the width of the catalyst layer 36 is gradually increased.

The catalyst layer 36 forms three

reaction zones

37, 38, 39 according to the

flow paths

33, 34, 35. When the thickness of the catalyst layer 36 is an average value of the distance between the heat transfer plates 2 in the direction perpendicular to the axis of the heat transfer plate 2, the thickness of the catalyst layer 36 in the reaction zone 37 is, for example, 8 to 15 mm. The thickness of the catalyst layer 36 in the reaction zone 38 following the reaction zone 37 is, for example, 10 to 20 mm, and the thickness of the catalyst layer 36 in the reaction zone 39 following the reaction zone 38 is, for example, 15 to 30 mm.

When performing the gas phase contact reaction using the plate reactor, the reaction temperature is controlled by the temperature of the heat medium flowing through the heat transfer tube 1. The temperature of the heating medium varies depending on the types of raw materials, products, and catalysts, but is generally preferably 200 to 600 ° C. An example of the temperature of the heat medium is 300 to 400 ° C. when the reaction raw material gas is a C3 to C4 unsaturated hydrocarbon. The temperature of the heating medium supplied to each reaction zone is independently determined and controlled. When the reaction raw material gas is (meth) acrolein, the temperature of the heat medium is selected in the range of 250 to 320 ° C.

Particularly, the reaction conversion rate of the reaction raw material gas is important, and the temperature of the heat medium is controlled in order to obtain a desired conversion rate. If the temperature of the catalyst layer is set to an allowable temperature or higher during the operation of the plate reactor, problems such as a decrease in the activity of the catalyst, a decrease in the selectivity, and an increase in the activity and the rate of decrease in the selectivity may occur. Here, the “conversion rate” refers to the ratio of the amount of the raw material gas converted into the product by the reaction with respect to the supply amount of the raw material gas (for example, propylene) supplied to the catalyst layer, and the “selectivity” The ratio of the amount of the raw material gas converted into the target product to the amount of the raw material gas converted by the reaction is said.

The temperature of the heating medium is controlled in order to obtain a predetermined conversion rate, but in order to keep the catalyst performance high over a long period of time, it is important that the maximum temperature of the catalyst layer is not more than the maximum allowable temperature of the catalyst used. More preferably, it is important to keep the maximum temperature of the catalyst layer as low as possible within a range where desired reaction results can be obtained.

The heat medium is supplied to each of the reaction zones 2 to 5 at a temperature at which the peak temperature of the catalyst layer is within the set value ± 10 ° C., and flows in a direction perpendicular to the reaction gas flow method (cross flow direction). The temperature difference of the heat medium at the inlet and outlet in one heat transfer tube 1 is preferably 0.5 to 10 ° C, more preferably 2 to 5 ° C. In the form shown in FIG. 11, the heat medium controlled to a predetermined temperature may flow, for example, for each one of the heat transfer tubes 1 in the flow paths 33 to 35, or all of the heat transfer tubes 1 in the same reaction zone. In some cases, it may flow simultaneously. It is also possible to supply the heat medium supplied to and discharged from the heat transfer tube 1 in a certain reaction zone to the heat transfer tube 1 in the same or another reaction zone.

There is a high possibility of being related to the reaction results, and as a notable production accuracy of the plate reactor, the thickness of the heat transfer tubes a to c that determines the thickness of the catalyst layer 36 (the distance between the surfaces of the heat transfer plate 2). And the distance between the axes of the pair of heat transfer plates 2. If the distance between the axes of the heat transfer plate 2 is constant and the thickness of the heat transfer tube 1 is too thin than the setting, or if the distance between the axes of the heat transfer plate 2 is too larger than the setting, the thickness of the catalyst layer 36 ( The distance between the surfaces of the heat plate 2) is increased, heat transfer is not performed efficiently, and the temperature of the catalyst layer 36 and the reaction raw material cannot be properly maintained.

If the distance between the axes of the heat transfer plate 2 is constant and the thickness of the heat medium flow path is too larger than the setting, or if the distance between the axes of the heat transfer plate 2 is too smaller than the setting, the thickness of the catalyst layer 36 ( The distance between the surfaces of the heat transfer plates becomes smaller and heat transfer becomes efficient, but the set catalyst cannot be charged correctly and the gas phase catalytic reaction may not be maintained correctly.

In the plate reactor, a heat medium of, for example, 345 ° C. is passed through the heat transfer tube 1 as a heat medium, and a gas containing propylene, molecular oxygen, water vapor, and an inert gas is flowed from the upper gas distributor 6 as a raw material gas. Thus, a reaction gas containing acrolein and acrylic acid is obtained. The raw material gas is supplied in the supply amount of the raw material gas for obtaining a desired yield of the reaction product determined from the design value, and the heat medium is supplied to the heat transfer tube 1 at the temperature and supply amount of the heat medium determined from the design value. The maximum temperature (peak temperature) A of the catalyst layer 36 is supplied and measured by the temperature measuring device 9.

When the peak temperature A is within the set value ± 10 ° C., the heat medium is supplied to the heat transfer tube 1 at the set temperature and supply amount of the heat medium. When the peak temperature A is higher than the set value + 10 ° C., the heat medium is supplied to the heat transfer tube 1 at a temperature lower than the set temperature of the heat medium and the set supply amount of the heat medium. When the peak temperature A is lower than the set value −10 ° C., the heat medium is supplied to the heat transfer tube 1 at a temperature higher than the set temperature of the heat medium and a set supply amount of the heat medium. Thus, by controlling the temperature of the heating medium according to the peak temperature of the catalyst layer 36, it is possible to continue producing the reaction product without changing the supply amount of the raw material gas and without reducing the reaction yield. .

Since the plate type reactor uses the heat transfer plate 2 formed by joining steel plates formed with an error with respect to the design value within ± 1%, the measured value of the peak temperature of the catalyst layer is the peak temperature. By controlling the temperature of the heating medium so as to be a set value, it is possible to maintain the production of the reaction product under conditions with high productivity.

In addition, since the plate type reactor has the partition 7, it is effective from the viewpoint of arranging the heat transfer plate 2 according to the design value of the distance between the surfaces of the heat transfer plate 2. Further, since the plate reactor has the partition 7, a plurality of sections are formed in the gap between the heat transfer plates 2, and the catalyst is filled in each section. Therefore, the catalyst is uniformly filled in the gap. It is effective from the viewpoint.

Further, since the plate type reactor has the temperature measuring device 9, the temperature of the catalyst layer 36 can be measured, and production with high efficiency is achieved by controlling the temperature of the heating medium according to the peak temperature of the catalyst layer 36. It is effective from the viewpoint of manufacturing a product.

Further, since the plate type reactor has a heat medium mixing device, it is effective from the viewpoint of controlling the temperature of the heat medium in the heat medium supply device 5 quickly and precisely.

Further, since the plate type reactor has the vent plug 8, it is possible to extract only the catalyst in an arbitrary section, which is effective from the viewpoint of uniformizing the catalyst layer 36 and improving the efficiency of maintenance and inspection work. It is.

The plate reactor has a gas distribution section 6 and a manhole 19, and the holding rod 4 is disposed at a position overlapping the partition 7. Therefore, the scaffold or support for the catalyst filling work and maintenance work is provided. The holding rod 4 can be used as a member, which is effective from the viewpoint of efficiently working inside the plate reactor.

In the first plate reactor, the width of the catalyst layer 43 for each of the three

reaction zones

40, 41, 42 formed along the flow direction of the raw material gas as disclosed in Patent Document 2. The form shown in FIG. 12 is also included.

Plate reactors are generally difficult to manufacture with high accuracy. For example, plate heat exchangers with similar configurations generally have an error of 3 to 5 mm or more with respect to the design value for the distance between the surfaces of the heat transfer plates. Have. In the first plate reactor, it is possible to provide a plate reactor in which the heat transfer plate is arranged within an error range in which the reaction can be controlled by controlling the temperature of the heat medium. The possibilities can be greatly expanded.

The first plate type reactor can be used for reactions in which gas phase raw materials are reacted in the presence of a solid phase catalyst. In particular, the temperature in the reactor at the time of use and operations for preparation and inspection can be performed. When used under conditions where the difference from room temperature is large, or when the source gas or product gas is exposed to the conditions at the time of use for a long time, the deterioration of these gases may cause damage to the reactor. This is more effective when the heat of reaction accompanying the reaction of the gas component is remarkably large and the catalyst is likely to be deteriorated by the heat, and the temperature control of the catalyst layer is important.

<Second plate reactor>
The second plate reactor has a reaction vessel for reacting reaction raw materials, a heat transfer tube, a plurality of heat transfer plates provided in line in the reaction vessel, and supplies a heat medium to the heat transfer tube And a partition that divides a gap between adjacent heat transfer plates into a plurality of compartments containing the filled catalyst along the aeration direction in the reaction vessel.

The reaction vessel includes a plurality of heat transfer plates arranged in parallel in the aeration direction in the reaction vessel, and a plurality of catalyst layers arranged in parallel in the aeration direction in the reaction vessel, wherein a catalyst is filled in a gap between adjacent heat transfer plates. Is formed. For the reaction vessel, for example, a casing having a rectangular cross section with respect to the aeration direction or a shell having a circular cross section is used.

The reaction vessel is a vessel in which the supplied reaction raw material is discharged through a gap between adjacent heat transfer plates, and usually has a pair of vent holes. One of the pair of vent holes serves as a supply port for the reaction raw material supplied to the reaction vessel, and the other serves as a discharge port for the reaction product generated in the reaction vessel. The form of the vent is not particularly limited as long as the reaction raw material is supplied to the reaction vessel and the reaction product is discharged from the reaction vessel. The pair of vent holes are preferably provided to face each other. As such a vent, for example, a pair of vents provided at both ends of a casing or a shell, or a cylindrical portion formed in a central portion including a central axis of the shell and an inner peripheral portion of the shell, respectively, the crossing of the shell A pair of vents that allow the reaction fluid to vent radially on the surface may be mentioned.

The heat transfer plate is formed in a plate shape including a plurality of heat transfer tubes connected in one direction at the peripheral edge or edge in the cross-sectional shape.

As disclosed in Patent Document 1, such a heat transfer plate is formed by forming two corrugated plates in which patterns such as arcs, elliptical arcs, and rectangles are continuously formed at the ends of the patterns of both corrugated plates. Can be formed by joining each other with convex edges. Alternatively, the heat transfer plate can be formed by connecting a plurality of the heat transfer tubes at a peripheral edge or an edge. Alternatively, the heat transfer plate can be formed by stacking a plurality of the heat transfer tubes so as to contact each other at the peripheral edge or the edge in the reaction vessel.

The shape of the heat transfer plate is determined according to the shape and size of the reaction vessel, but is generally rectangular. The size of the heat transfer plate is determined according to the shape and size of the reaction vessel. For example, in the case of a rectangular heat transfer plate, the length (that is, the connection height of the heat transfer tubes) is 0.5 to It is 5 m, more preferably 1 to 3 m, and the width (ie, the length of the heat transfer tube) is 0.05 to 10 m, more preferably 1 to 10 m. However, there is usually no limitation in the horizontal direction.

Adjacent heat transfer plates in the reaction vessel may be arranged so that the convex edges of the surface of the heat transfer plate face each other, or the convex edges of the surface of one heat transfer plate are the surfaces of the other heat transfer plate. You may arrange so that a concave edge may be opposed. The distance between adjacent heat transfer plates is such that a gap with a width of 3 to 40 mm, more preferably 3 to 15 mm is formed between the heat transfer plates in the transverse direction of the heat transfer tubes. The average distance between the major axes is 15 to 50 mm, more preferably 23 to 50 mm (1.1 to 5 times the sum of the half value of the width of the heat transfer tubes in adjacent heat transfer plates, more preferably 1.1 to 2 Times). The distance between the heat transfer plates is preferably 10 to 50 mm, more preferably 10 to 40 mm in terms of the average distance of the long axis tubes of the heat transfer tube from the viewpoint of obtaining a high reaction rate and high reaction results. More preferably, the thickness is 20 to 35 mm.

The heat transfer tube in the heat transfer plate is not formed so as to extend in a direction parallel to the aeration direction in the reaction vessel, but the reaction of the raw material is controlled by adjusting the temperature of the heat medium in the heat transfer tube. It is preferable from the viewpoint, and is formed so as to extend in a direction orthogonal to the aeration direction in the reaction vessel, that is, a direction in which the direction of the heat medium flowing through the heat transfer tube is orthogonal to the aeration direction in the reaction vessel. It is more preferable from the viewpoint of controlling the reaction of the raw material by adjusting the temperature of the heat medium in the heat transfer tube.

The heat transfer tube is formed of a material having a heat transfer property in which heat is exchanged between a heat medium in the heat transfer tube and a catalyst layer circumscribing the heat transfer tube. Examples of such a material include stainless steel and carbon steel. The cross-sectional shape of the heat transfer tube may be a circle, a substantially circular shape such as an elliptical shape or a rugby ball shape, or a rectangular shape. 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 long axis end in a substantially circular shape or a single edge in a rectangle.

The shape and size of the cross section of each of the plurality of heat transfer tubes in one heat transfer plate may be constant or different. The size of the cross-sectional shape of the heat transfer tube is, for example, a width of the heat transfer tube of 3 to 50 mm, more preferably 3 to 20 mm or 5 to 50 mm, and a height of the heat transfer tube of 10 to 100 mm, more preferably 10 to 50 mm or 20 to 100 mm.

If the heat transfer tube width is small per unit time or per unit area of heat transferred by the heat transfer plate, increase the catalyst layer thickness by increasing the catalyst layer thickness and increasing the catalyst layer to increase the reaction rate. From the viewpoint, it is more preferably 3 to 20 mm, and when the amount of heat per unit time or unit area transferred by the heat transfer plate is large, the thickness of the catalyst layer is reduced to improve heat transfer, and the amount of catalyst is reduced. From the viewpoint of reducing the reaction rate, it is more preferably 5 to 50 mm. In addition, when the heat transfer tube has a small amount of heat per unit time or unit area transferred by the heat transfer plate, the catalyst layer is increased by increasing the thickness of the catalyst layer and increasing the catalyst layer to increase the reaction rate. In view of the above, it is more preferable that the thickness is 10 to 50 mm. When the amount of heat per unit time or unit area transferred by the heat transfer plate is large, the thickness of the catalyst layer is reduced to improve heat transfer, and the amount of catalyst is reduced. From the viewpoint of reducing the reaction rate by reducing the thickness, it is more preferably 20 to 100 mm.

The heat medium supply device may be any device that supplies a heat medium to the heat transfer tube. As such a heat medium supply device, for example, a device that supplies a heat medium in one direction to all of the plurality of heat transfer tubes, or a heat medium that supplies a heat medium in one direction to a part of the plurality of heat transfer tubes. Another part of the heat pipe includes a device for supplying a heat medium in the reverse direction. The heat medium supply device is preferably a device that circulates the heat medium inside and outside the reaction tube via the heat transfer tube. The heat medium supply device preferably has a device for adjusting the temperature of the heat medium from the viewpoint of controlling the reaction in the reaction vessel.

The partition is provided in a gap between adjacent heat transfer plates along the aeration direction in the reaction vessel, and forms a plurality of compartments in the gap. The partition may be a member that can hold a catalyst in each compartment when the catalyst is filled in each compartment. The partition is preferably formed of the same material as the heat transfer plate, preferably has heat transfer properties, preferably not reactive to the reaction in the reaction vessel, and the reaction in the reaction vessel is an exothermic reaction. In some cases, it is preferable to have heat resistance. The partition preferably has rigidity from the viewpoint of holding the catalyst filled in each compartment. Examples of such partitions include stainless steel plates, square bars, round bars, nets, glass wool, and ceramic plates.

The shape of the partition is not particularly limited as long as the catalyst is held in the partition formed by each partition, and may be a shape in contact with the heat transfer tube or a shape in close contact with the heat transfer tube. Further, the partition preferably has a shape in contact with the surface of the outer wall of each heat transfer tube, from the viewpoint of holding the catalyst filled in each section, and has a shape that closely contacts the surface of the outer wall of the heat transfer tube. More preferred. Moreover, it is preferable that the said partition is a shape which becomes a square which has the width | variety of the shortest distance between the heat exchanger plates which a front view adjoins from a viewpoint which installs a partition easily.

The partition is preferably provided at an interval of 1 to 100 L from the viewpoint that the volume of the compartment formed by the partition can be accurately and easily filled with the catalyst in one compartment. The volumes of the compartments formed by the partitions may be the same or different, but are preferably the same from the viewpoint of accurate and easy filling of the catalyst into all the compartments. The volume of the one compartment is more preferably 1.5 to 30 L, further preferably 2 to 15 L, still more preferably 3 to 15 L, and still more preferably 5 to 10 L. . Further, the distance between the partitions (the interval between the partitions) is preferably 0.1 to 1 m from the same viewpoint. The interval between the partitions is the length of the partition in the axial direction of the heat transfer tube, and the distance between adjacent partitions forming the partition, or the heat transfer tube forming the partition is connected. This is the distance between the inner wall surface of the reaction vessel and the partition.

The partition can be provided in the gap between the heat transfer plates as appropriate according to the properties of the partition. For example, a flexible partition or a partition having the shortest distance between the heat transfer plates is inserted into a gap between adjacent heat transfer plates in a plurality of heat transfer plates installed in the reaction vessel in advance. Therefore, it can be provided in the gap between the heat transfer plates. In addition, when the heat transfer plate is installed in the reaction vessel, the partition having a shape closely contacting the surface of the heat transfer plate can be provided in the gap between the heat transfer plates by alternately installing the heat transfer plate and the partition. it can.

As the catalyst filled in the compartment, a normal granular catalyst filled in a gap between a tube or a heat transfer plate by a gas phase reaction can be used. One or more catalysts may be used. Examples of such a catalyst include a catalyst having a particle diameter (longest diameter) of 1 to 20 mm, and a catalyst having a particle diameter (longest diameter) of 3 to 20 mm and a specific gravity of 0.7 to 1.5. It is done. Moreover, as a shape of a catalyst, a well-known thing can be used, for example, spherical shape, cylindrical shape, Raschig ring shape, and saddle shape are mentioned. In the case where the shape of the catalyst is formed so that the partition is not in close contact with the surface of the heat transfer plate, the catalyst has a shape with the shortest diameter larger than the gap between the heat transfer plate and the partition. This is preferable from the viewpoint of preventing leakage of the catalyst, and when the partition is formed in a shape that does not adhere to the surface of the heat transfer plate, it is 1.2 to 2 times the maximum value of the gap between the partition and the heat transfer plate. A shape having a minimum diameter is more preferable.

The filling of the catalyst into the gap between the adjacent heat transfer plates is performed by filling the catalyst into each section. Each compartment can be filled with a catalyst by filling the same volume of catalyst in a compartment continuously or intermittently. The appropriate filling state of the catalyst is, for example, the comparison of the position of the top surface of the packed catalyst (catalyst layer) between the compartments, the measured value of the top surface in each compartment, and the calculated value of the top surface of each compartment. This can be determined by comparison.

The second plate reactor may further have other components other than the components described above. Such other components include, for example, air permeability, provided at the end of the heat transfer plate on the downstream side in the aeration direction in the reaction vessel, and leakage of the packed catalyst from the reaction vessel. Leakage prevention member (for example, vent plug) for preventing, and locking member (at the partition for fixing the partition) provided at one end of the partition and latched on the leakage prevention member or heat transfer plate Locking part).

The vent plug is a member that achieves both the breathability of each section and the retention of the catalyst, and is a member that is detachably fixed to the end of each section in the ventilation direction. The vent plug may be provided at the upstream end portion in the ventilation direction in each compartment or may be provided at the downstream end portion as long as it can prevent leakage of the catalyst from each compartment. These may be provided at both ends. In addition, the entire vent plug may have air permeability, or may have air permeability only in the ventilation direction of each section. Note that the aeration generally means that a gas that is one of the states of the reaction raw material or the reaction product passes, but in this specification, the state of the reaction raw material or the reaction product is a fluid other than a gas ( For example, in the case of liquid), this means that the fluid passes through.

The vent plug preferably has an opening ratio of 10% or more in the ventilation direction of each section from the viewpoint of ensuring air permeability in each section. The opening ratio is more preferably 20% or more, and further preferably 30% or more, from the viewpoint of preventing the occurrence of pressure loss when the vent plug is fixed to the end of the compartment.

In addition, from the viewpoint of holding the catalyst in each compartment, the vent plug preferably has a hole diameter of 5 mm or less, more preferably 3 mm or less, and even more preferably 1 mm or less.

The vent plug can be composed of one or more members having air permeability. As the vent plug, for example, a vent plate such as a plate-like net or a perforated plate; a vent cylinder having a shape obtained by forming the vent plate into a cylindrical shape; and a vent plate on a part or all of the periphery of the vent plate A member having a skirt portion provided perpendicularly to the first section; a first through-cylinder having a circular or rectangular cross-sectional shape; and a second through-cylinder housed inside the first through-cylinder and slidable A breathable double tube having: The cylinder, the member having the skirt portion, and the breathable double pipe are preferable from the viewpoint of obtaining sufficient strength for holding the catalyst. The member having the skirt portion is more preferable from the viewpoint of easily attaching and detaching the end portion of each section.

In the member having the skirt portion, the vent plate preferably has the same shape as the cross-sectional shape of each section from the viewpoint of preventing catalyst leakage from each section. The skirt portion is provided on a part of the periphery of the ventilation plate, for example, as a pair of skirt portions that are in contact with the opposing partition or heat transfer plate in each section, from the viewpoint of easily detachably fixing the vent plug Preferably, it is provided on the entire periphery of the vent plate from the viewpoint of increasing the strength of the vent plug. In addition, the skirt portion may be provided so as to protrude on both sides of the ventilation plate, or may be provided so as to protrude only on one side of the ventilation plate.

The vent plug is detachably fixed at the end of each compartment. The structure for detachably fixing the partition side, that is, from the viewpoint of easily fixing and removing the vent plug and fixing the vent plug with sufficient strength to hold the catalyst, that is, the heat transfer plate and the partition. It is preferable that it is the 1st latching | locking part provided in one or both of this, and the 2nd latching | locking part provided in a vent plug detachably latched with this 1st latching | locking part. As a 1st and 2nd latching | locking part, the nail | claw currently urged | biased in the direction which advances to a hole and this hole, a hole, a volt | bolt, a nut, etc. are mentioned, for example. From the viewpoint of preventing seizure when the temperature of the reaction vessel is relatively high, it is preferable that the first and second engaging portions have a simple configuration such as the hole and the claw.

The vent plug is formed of a material having sufficient rigidity for holding the catalyst. Examples of such materials include metals such as stainless steel and ceramics. The vent plug is preferably formed of the same material as the heat transfer plate from the viewpoint of heat resistance and reaction resistance.

Further, the catalyst filled in each compartment can be extracted in units of compartments by removing the vent plug and taking out the catalyst from the end of the compartment.
Hereinafter, the plate reactor of the present invention will be described more specifically with reference to the drawings.

<Second Embodiment>
For example, as shown in FIGS. 13 to 15, the second plate reactor includes a rectangular casing 44 and a plurality of heat transfer plates 2 that have the heat transfer tubes 1 and are provided facing each other in the casing 44. A plurality of compartments in which the catalyst is filled and held along the air flow direction in the casing 44 in the gap between the heat medium accommodating portion 45 for accommodating the heat medium supplied to the heat transfer tube 1 and the adjacent heat transfer plates 2. A plurality of partitions 7, perforated

plates

10, 46 provided at the upper and lower portions of the heat transfer plate 2, a pump 15 for circulating the heat medium in the heat medium accommodating portion 45, and the temperature of the circulating heat medium And a temperature adjusting device 47 for adjusting.

The casing 44 forms an air passage having a rectangular cross-sectional shape, and corresponds to the reaction vessel. The casing 44 has a pair of opposed vent holes 48, 48 ′ at the upper end and the lower end of the casing 44. The heat transfer tube 1 is, for example, a tube having a major axis of 30 to 50 mm and a minor axis of 10 to 20 mm and an elliptical cross section.

The heat transfer plate 2 has a shape in which a plurality of heat transfer tubes 1 are connected by an edge having a cross-sectional shape. The heat transfer plate 2 is formed by joining two corrugated plates each having an elliptical arc formed continuously with a convex edge formed at the ends of the arcs of both corrugated plates. The adjacent heat transfer plates 2 may be arranged in parallel so that the convex edges of the surfaces face each other, but in the plate reactor of FIG. 13, the convex edges of the surface of one heat transfer plate 2 and the other The heat transfer plates 2 are arranged in parallel so as to face the concave edges on the surface.

As shown in FIG. 16, for example, the heat transfer plate 2 includes three types of heat transfer tubes a to c having different cross-sectional sizes in the upper part, the middle part, and the lower part. The heat transfer plate 2 is formed so that the long axes of the heat transfer tubes a to c are arranged in a straight line. Further, for example, the heat transfer tube a forms the heat transfer plate 2 for 20% of the height of the heat transfer plate 2, and the heat transfer tube b forms the heat transfer plate 2 for 30% of the height of the heat transfer plate 2. The heat transfer tube c forms the heat transfer plate 2 for 40% of the height of the heat transfer plate 2. 10% of the height of the heat transfer plate 2 is formed by the upper and lower joint plate portions of the heat transfer plate 2.

The cross-sectional shape of the heat transfer tube a formed on the upper part of the heat transfer plate 2 is an ellipse having a major axis of 50 mm and a minor axis of 20 mm. The cross-sectional shape is an ellipse having a major axis of 40 mm and a minor axis of 16 mm, and the sectional shape of the heat transfer tube c formed at the lower part of the heat transfer plate 2 is a major axis of 30 mm and a minor axis of 10 mm. It is oval.

The heat transfer plates 2 may be arranged in parallel at different intervals in the entire reaction vessel, but in the plate reactor of FIG. 13, the same interval (for example, the shortest distance between the outer walls of the heat transfer tube a is 14 mm (each The distance between the major axes of the heat transfer tubes of the heat plate 2 is 30 mm)).

The heat medium accommodating portion 45 is a container provided on a pair of opposing walls of the casing 44, and a supply port for supplying a heat medium to each heat transfer tube 1 is formed in the wall. The heat medium is divided into a plurality at a predetermined height so that the heat medium meanders between the heat medium accommodating portions 45 via the heat transfer tubes 1.

The partition 7 is provided between the adjacent heat transfer plates 2 along the ventilation direction in the casing 44. The partitions 7 may be provided at different intervals in the entire reaction vessel, but in the plate type reactor of FIG. 13, a partition having a volume of 23 L is formed in parallel at the same interval (for example, 1,000 mm). . The interval between the partitions 7 is preferably 5 cm to 2 m, and more preferably 10 cm to 1 m. The volume of the partition between 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 gap into the gap in units of units and accurately and easily filling the catalyst. It is more preferable.

A member that can hold the filled catalyst in each compartment when the catalyst is filled in each compartment is used for the partition 7. As the partition 7, for example, as shown in FIGS. 17 to 19, a plate or net having a shape having a side edge that is in close contact with the unevenness on the surface of the heat transfer plate 2 can be used.

In addition, the partition 7 is in contact with the heat transfer tube a of the adjacent heat transfer plate 2 if the catalyst filled in each partition does not leak from the gap between the partitions 7 to the adjacent partition. A member that does not come into contact with the convex and concave edges of the heat transfer tubes b and c can be used. For example, as shown in FIGS. 20 and 21, a round having the shortest distance diameter or width between adjacent heat transfer plates 2. A stick or a square stick can be used.

Furthermore, as shown in FIG. 18, the partition 7 may be a net having an eye smaller than the size of the catalyst particles to be filled, or if the catalyst filled in each compartment does not leak into the adjacent compartment, As shown in FIG. 19, it may be a mesh having larger eyes than the catalyst particles (for example, 0.8 times or less of the shortest diameter of the catalyst).

In the case where two adjacent heat transfer plates 2 are arranged in parallel so that the convex edge of one heat transfer plate 2 faces the concave edge of the other heat transfer plate 2, the partition 7 has a partition as shown in FIG. In addition, a zigzag plate or net that protrudes toward the concave edge of the heat transfer plate 2 at the side edge of the partition 7 and is separated from the convex edge of the heat transfer plate 2 can be used. Such a partition 7 has a distance between two heat transfer plates 2 arranged in parallel so that one convex edge faces the other concave edge (an average of distances between major axes of the heat transfer tubes 1 in each heat transfer plate 2). Can be suitably used when the value is 0.9 to 1.5 times the sum of the half-values of the maximum short diameters of the heat transfer tubes in each heat transfer plate 2.

17 to 19 and 22, the partition 7 having a shape having a side edge in contact with the unevenness of the surface of the heat transfer plate 2 is used when the heat transfer plate 2 is installed in the casing 44. By alternately installing the abutment partitions 7, they are provided between the two heat transfer plates 2. The partition 7 having the shortest distance diameter or width between the adjacent heat transfer plates 2 as shown in FIGS. 20 and 21 is formed by alternately installing the heat transfer plates 2 and the partitions 7 in contact with the partitions 7. You may provide between the heat-transfer plates 2, and you may provide by inserting between the heat-transfer plates 2 adjacent to the heat-transfer plate 2 already installed. The flexible partition 7 such as a net or a thin steel plate can also be provided by inserting it between the adjacent heat transfer plates 2 of the heat transfer plates 2 already provided.

The

perforated plates

10 and 46 are plates each having a hole having a diameter of 0.20 to 0.99 times the longest diameter of the catalyst to be filled with an opening ratio of 20 to 99%. In the plate reactor of FIG. 13, the

perforated plates

10, 46 are shown in FIG. 15 in order to prevent air from flowing into the gap between the outermost heat transfer plate 2 and the wall of the casing 44. Thus, it is formed so as to close the gap from the edge of the heat transfer plate 2 arranged on the outermost side to the wall of the casing 44.

A device capable of transferring a heat medium having a desired temperature is used for the pump 15. The temperature adjusting device 47 is a device such as a heat exchanger that can control the temperature of the heat medium to a desired temperature. The heat medium storage unit 45, the pump 15, and the temperature adjustment device 47 constitute a heat medium supply device.

The filling of the catalyst between the heat transfer plates 2 is performed by filling each compartment with the catalyst. Since all of the compartments formed by the heat transfer plate 2 and the partition 7 have the same volume, the capacity equivalent to the capacity of one compartment (for example, a volume of 95 to 100% with respect to the capacity of one compartment) Of each catalyst is packed into each compartment.

The good packing state of the catalyst means comparison between the theoretical value of the height when a predetermined amount of catalyst is filled and the measured value (for example, the error of the measured value with respect to the theoretical value is within 10%), and the catalyst between the compartments. Can be determined by comparison of the filling heights (for example, the difference in filling height between the sections is within 2% of the filling height).

The partition 7 has a hook that engages with an engagement portion such as a hole or a ring provided in the hole of the perforated plate 46 or the end of the heat transfer plate 2, and the hook is locked to the engagement portion. By extending the partition 7 by this, it is also possible to provide in the gap between the adjacent heat transfer plates 2. According to such a structure, it becomes possible to use for the partition 7 the material which does not have shape retention property, such as glass wool.

Since the plate type reactor has the partition 7, the catalyst can be uniformly filled in the entire reactor by filling the catalyst in a fixed state in units of compartments. Therefore, compared with the catalyst filling between the heat transfer plates 2 in which such compartments are not formed, the amount of the catalyst is accurately compared to the design value, and the filling state between the compartments (for example, packing density, porosity) Can be more easily performed.

In the plate type reactor, since all the sections formed by the heat transfer plate 2 and the partition 7 have the same capacity, the catalyst used for one catalyst filling operation is constant. Therefore, the filling operation of the catalyst can be performed more rapidly than the filling of the catalyst between the heat transfer plates 2 in which such a partition is not formed.

Furthermore, since the plate type reactor has the partition 7, it is possible to judge the packing state of the catalyst in units of compartments. Therefore, when the catalyst filling state is poor, it is possible to correct the catalyst filling state by refilling only the catalyst in the section determined to be defective. Therefore, the catalyst filling operation can be adjusted more easily than the catalyst filling between the heat transfer plates 2 in which such compartments are not formed.

<Third embodiment>
The second plate reactor, for example, as shown in FIGS. 23 to 25, except that the perforated plate 46 has a plurality of vent plugs 8 that have air permeability and close the lower end portions of the respective sections. It has the same configuration as the plate reactor of the second form.

In the present embodiment, the casing 44 forms an air passage having a rectangular cross-sectional shape and corresponds to the reaction vessel. The casing 44 has a pair of opposed vent holes 48, 48 ′ at the upper end and the lower end of the casing 44, a casing end portion 49 including the vent port 48, and a casing end portion 49 ′ including the vent port 48 ′. And a casing body in which the heat transfer plate 2 is accommodated. The casing end portions 49 and 49 'are detachably connected to the casing body. The heat transfer tube 1 is, for example, a tube having a major axis of 20 to 100 mm and a minor axis of 5 to 50 mm and an elliptical cross section.

The heat transfer plate 2 has a shape in which a plurality of heat transfer tubes 1 are connected by an edge having a cross-sectional shape. The heat transfer plate 2 is formed by joining two corrugated plates each having an elliptical arc formed continuously with a convex edge formed at the ends of the arcs of both corrugated plates. The adjacent heat transfer plates 2 may be arranged in parallel so that the convex edges of the surfaces face each other, but in the plate reactor of FIG. 23, the convex edges of the surface of one heat transfer plate 2 and the other The heat transfer plates 2 are arranged in parallel so as to face the concave edges on the surface.

As shown in FIG. 16, for example, the heat transfer plate 2 includes three types of heat transfer tubes a to c having different cross-sectional sizes in the upper part, the middle part, and the lower part. The heat transfer plate 2 is formed so that the long axes of the heat transfer tubes a to c are arranged in a straight line. In this embodiment, for example, the heat transfer tube a forms the heat transfer plate 2 corresponding to 30% of the height of the heat transfer plate 2, and the heat transfer tube b corresponds to 25% of the height of the heat transfer plate 2. The heat plate 2 is formed, and the heat transfer tube c forms the heat transfer plate 2 for 45% of the height of the heat transfer plate 2.

In the present embodiment, the heat transfer plates 2 may be arranged in parallel at different intervals in the entire reaction vessel, but in the plate reactor of FIG. 23, the same interval (for example, the shortest distance between the outer walls of the heat transfer tubes a) is used. Are parallel to each other at 5 mm (the distance between the major axes of the heat transfer tubes of each heat transfer plate 2 is 25 mm).

The heat medium accommodating part 45 is the same as the heat medium accommodating part 45 in the second embodiment.

The partition 7 is provided between the adjacent heat transfer plates 2 along the ventilation direction in the casing 44. The partitions 7 may be provided at different intervals in the entire reaction vessel. However, in the plate reactor of FIG. 23, the partitions 7 are arranged in parallel at the same interval (for example, 500 mm) to form a 25 L volume compartment. In the present embodiment, for example, 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 2 as shown in FIG. 26, and has a window 20 at the lower end. Yes.

The vent plug 8 is provided at the lower end of each section as shown in FIG. For example, as shown in FIG. 28, the vent plug 8 includes a rectangular vent plate 21 having the same cross-sectional shape in each section, a first skirt portion 22 suspended downward from the short side of the vent plate 21, and a vent plate 21 and a second skirt portion 23 that hangs downward from the long side. As shown in FIG. 28, the first skirt portion 22 is formed with a rectangular locking window 24 and a locking claw 50 provided adjacent thereto.

As shown in FIG. 29, the vent plug 8 has a shape in which the ventilation plate 21 and the

skirt portions

22 and 23 are developed, and the skirt portion 22 has a notch that becomes a locking window 24 and a locking claw 50. The formed stainless steel plate is bent at the boundary between the ventilation plate 21 and the

skirt portions

22 and 23, and the edges of the skirt portions are welded. The ventilation plate 21 is, for example, a plate in which circular holes of 2 mm are formed with an opening rate of 30%.

In the first skirt portion 22, the locking claw 50 is formed by bending two parallel cuts from the lower end edge of the first skirt portion 22 so as to protrude outward. In each of the first skirt portions 22, the locking window 24 and the locking claw 50 are provided in the same positional relationship with respect to the ventilation plate 21. Accordingly, in the pair of first skirt portions 22 that face each other, one locking window 24 and the other locking claw 50 face each other, and one locking claw 50 and the other locking window 24 face each other. Yes. The locking window 24 is formed in a size having a width and a height for accommodating the locking claw 50, and the window 20 of the partition 7 includes the locking window 24 and the locking claw 50 at the same time. It is formed in a size having a width and a height.

The vent plug 8 is inserted into each section from the lower end of each section with the ventilation plate 21 up. At this time, the locking claw 50 is pressed by the partition 7 against the outward bias, but when it reaches the window 20, it is released from the pressing of the partition 7 and reaches the window 20 as shown in FIG. 30. Advancing toward and locking to the window 20. The window 20 corresponds to a first locking portion, and the locking claw 50 corresponds to a second locking portion.

In this embodiment, the perforated plate 10 is a plate in which holes having a diameter of 0.3 to 0.8 times the longest diameter of the catalyst to be filled are provided with an opening ratio of 20 to 40%. . In the plate reactor shown in FIG. 23, the perforated plate 10 is used as shown in FIG. 25 in order to prevent air from flowing into the gap between the outermost heat transfer plate 2 and the wall of the casing 44. The outermost heat transfer plate 2 is formed so as to close the gap from the edge of the heat transfer plate 2 to the wall of the casing 44.

The pump 15 and the temperature adjusting device 47 are the same as the pump 15 and the temperature adjusting device 47 in the first embodiment. The heat medium storage unit 45, the pump 15, and the temperature adjustment device 47 constitute a heat medium supply device.

The filling of the catalyst between the heat transfer plates 2 is performed by filling each compartment with the catalyst. Since all the sections formed by the heat transfer plate 2 and the partition 7 have the same volume, in this embodiment, for example, a capacity equivalent to the capacity of one section (for example, the capacity of one section) 97 to 103% volume) of catalyst is loaded into each compartment.

In this embodiment, the good packing state of the catalyst is a comparison between the theoretical value of the catalyst filling height and the actual measurement value (for example, the error of the actual measurement value with respect to the theoretical value is within 3%), It can be determined by comparing the filling height (for example, the difference in filling height between the sections is within 5% of the filling height).

When the packing state of the catalyst in one section is poor, the vent plug 8 of the section is removed, and only the catalyst filled in the section is extracted from the lower end of the section. Since the window 20 of the partition 7 is formed in a size including the locking window 24 and the locking claw 50 when the vent plug 8 is fixed, the windows 20 are adjacent to each other via the partition 7. It opens to the locking window 24 and the locking claw 50 of the two vent plugs 8. Further, since the locking window 24 is formed in a size including the locking claw 50, one locking window 24 in the two vent plugs 8 adjacent to each other via the partition 7 is connected to the other locking claw 50. The other locking window 24 is open to one locking claw 50. In this way, the locking claw 50 that is locked is not blocked by the adjacent vent plug 8 with respect to the lower space of the ventilation plate 21, so that the engagement claw 50 is engaged in the lower space of the ventilation plate 21. The pawl 50 can be pushed directly. Therefore, the vent plug 8 uses, for example, a tool having a hook that can be inserted into the locking window 24 at the tip as shown in FIG. 31, and the locking window 24 and the partition 7 of the adjacent ventilation plug 8 through the partition 7. The locking claw 50 can be removed by pushing the locking claw 50 through the window 20 with the scissors and releasing the locking between the locking claw 50 and the window 20.

When the catalyst is extracted, the vent plug 8 is inserted and fixed again from the lower end of the compartment, and the catalyst is filled in the compartment, whereby the catalyst in each compartment can be filled again.

Since the plate type reactor has the partition 7, the catalyst can be uniformly filled in the entire reactor by filling the catalyst in a fixed state in units of compartments. Therefore, accurate filling of the catalyst can be performed more easily than the filling of the catalyst between the heat transfer plates 2 in which such a partition is not formed.

Further, since the plate reactor has the vent plug 8, the catalyst can be easily extracted in units of compartments. Therefore, if the packing state of the catalyst is poor, remove the vent plug of the section judged to be defective, remove the catalyst from the section, and refill the section with the catalyst to fill the catalyst in the specific section. The state can be easily corrected. Therefore, the catalyst filling operation can be more easily adjusted as compared with the catalyst filling between the heat transfer plates 2 in which such compartments are not formed.

Further, since the vent plug 8 has the rectangular vent plate 21 and the first and

second skirt portions

22 and 23, it is excellent from the viewpoint of obtaining sufficient strength to support the catalyst layer in each section. Moreover, since the vent plug 8 is obtained by stamping, bending, and welding a steel plate, such an excellent vent plug 8 can be easily obtained.

The vent plug 8 has a locking window 24 and a locking claw 50 in each of the pair of first skirt portions 22 facing each other, and one locking window is formed in the pair of first skirt portions 22 facing each other. 24 and the other locking claw 50 face each other, and one locking claw 50 and the other locking window 24 face each other. The latching claw 50 protruding from the top does not overlap or come into contact, and is excellent in terms of fixing the vent plug 8 with sufficient strength and easily removing the vent plug 8.

Further, since the window 20 of the partition 7 is formed in a size including the locking window 24 and the locking claw 50 when the vent plug 8 is fixed, any of the two vent plugs 8 in contact with the partition 7 can be obtained. The locking claw 50 is also detachably locked. As described above, the plate reactor is provided with the partition 7 having a single standard window 20, and therefore is excellent in terms of constructing the detachable structure of the vent plug 8 at low cost.

In the plate type reactor, the vent plug 8 is fixed by a contact with a small contact area between the locking claw 50 and the window 20 below the ventilation plate 21, so that the temperature is relatively high as in the oxidation reaction. From the viewpoint of preventing seizure between the locking claw 50 and the window 20 when used in the reaction under the above conditions.

In the plate reactor, the window 20 as the second locking portion is provided in the partition 7, but even if such a second locking portion is provided at the lower end of the heat transfer plate 5, A vent plug 8 can be provided in the same manner as in the plate reactor of FIG. Thus, even if there is no partition, a vent plug can be locked also by detachably fixing using the lower end part of the heat-transfer plate 5. FIG. Furthermore, you may provide a 2nd latching | locking part in both the lower end part of the partition 7, and the lower end part of the heat-transfer plate 5, and it is effective from a viewpoint of raising the fixing strength of a vent plug in this case.

In addition, for the partition, for example, various partitions may be used depending on the type and location of the second locking portion, the size of the gap generated between the partition and the heat transfer plate, and the distance between the heat transfer plates. it can. As such a partition, for example, as shown in FIGS. 18 and 19, a net having a side edge that is in close contact with the unevenness of the surface of the heat transfer plate 2, the diameter or width of the shortest distance between adjacent heat transfer plates 2. 20 and 21 and round bars and square bars as shown in FIGS. 20 and 21, as shown in FIG. 22, the side edge of the partition 7 protrudes toward the concave edge of the heat transfer plate 2, and the convexity of the heat transfer plate 2. Examples thereof include a zigzag plate or net spaced from the edge, and a member made of a material having no shape-retaining property such as glass wool.

In this embodiment, the partition as shown in FIGS. 18 and 19 is, for example, a mesh having a size that prevents the catalyst from leaking (for example, 0.5 times the longest diameter of the catalyst). The following can be suitably used. The size of the mesh used for the partition is preferably 0.8 or less times the minimum diameter of the catalyst.

20 and 21 can be suitably used in the present embodiment when a gap with such a width that the catalyst leaks is not formed between the heat transfer plate and the partition. Further, in the present embodiment, the partition as shown in FIG. 22 is a distance between two heat transfer plates 2 arranged in parallel so that one convex edge faces the other concave edge (the heat transfer tube in each heat transfer plate 2). 1 (the average value of the distances between the major axes) is 0.9 to 1.5 times the sum of the half-values of the maximum short diameters of the heat transfer tubes in each heat transfer plate 2. .

For the partition, for example, when the second locking portion is not provided in the partition, any of the above-described partitions can be used. For example, when the second locking portion is a window, a plate-like member that can provide a window that can support the vent plug can be used. For example, when the second locking portion is a window, a net-like member having a sufficiently large eye used as the window can be used for the partition.

As shown in FIGS. 26, 18, 19, and 22, the partition having a shape having a side edge in contact with the unevenness of the surface of the heat transfer plate comes into contact with the heat transfer plate when the heat transfer plate is installed in the casing. It is provided between two heat transfer plates by alternately installing partitions. As shown in FIGS. 20 and 21, the partition having the shortest distance diameter or width between adjacent heat transfer plates is formed by alternately arranging the heat transfer plates and the partitions contacting the heat transfer plates. Or may be provided by inserting between adjacent heat transfer plates of the already installed heat transfer plate. A flexible partition such as a net, cloth, or thin steel plate can be provided by inserting between adjacent heat transfer plates of the already installed heat transfer plate.

The partition has a hook that hooks to a further locking portion such as a hole or a ring provided in the hole of the vent plug 8 or the end of the heat transfer plate 2, and the hook is locked to the locking portion. It is also possible to provide a partition between the adjacent heat transfer plates 2 by stretching the partition. Such a configuration is preferable from the viewpoint of using a material having no shape-retaining property such as glass wool for the partition.

In addition, as shown in FIG. 32, a vent plug having a locking claw 51 whose tip is in contact with the lower end surface of the window 20 may be used for the vent plug 8 in the plate reactor. it can. Such a vent plug is even more excellent in terms of firmly fixing the vent plug to each compartment. The vent plug having the locking claw 51 is also effective from the viewpoint of preventing the vent plug from dropping and dropping the catalyst from the gap between the heat transfer plates even during long-term use of the plate reactor.

Also, if the vent plug has an appropriate detachable structure such as the window 20 and the locking claw 50, various forms of vent plugs can be used. As such a vent plug, for example, a cylinder formed of a net or a vent plate as shown in FIG. 33, a plate having a vent as shown in FIG. 34, a vent plate or a net as shown in FIGS. Examples include a member having a shape supported by a pair of skirt portions, and a box-shaped member having a surface formed of a net as shown in FIGS.

Furthermore, in another form of vent plug based on such a form, as shown in FIG. 39, a first vent pipe 52 having air permeability with respect to the ventilation direction of each section, and a ventilation direction of each section. And a double-pipe structure vent plug having a second vent pipe 53 that has air permeability and is slidable inside the first vent pipe 52. When such a vent plug is used, for example, the partition 7 is provided with a flange portion 54 that protrudes from the surface of the lower end portion of the partition 7, and the vent plug is extended until it contacts the partition 7 at both ends and is placed on the flange portion 54. By fixing the expansion and contraction of the vent plug in the sliding direction by the fixing pin 55, the vent plug is installed at the lower part of each section.

The fixing pin 55 includes, for example, a fixed shaft, a ring provided at one end thereof, and a flexible metal thin plate provided at the other end in a direction orthogonal to the extending direction of the fixed shaft. . When the fixing pin 55 is inserted from the vent hole on the lower surface of the vent plug, the metal thin plate bends when passing through the vent hole. A state is formed. Further, by pulling the ring of the fixing pin 55, the fixing pin 55 is pulled out by passing through the vent hole while the metal thin plate is bent, and further, the second vent pipe 53 is slid to lower the heat transfer plate. The vent plug can be removed.

Alternatively, in the other embodiment of the vent plug, a first vent pipe 52, a second vent pipe 53, and a second vent pipe 53 project from the first vent pipe 52 as shown in FIG. A vent plug having a biasing member 56 such as a coil spring that biases in the direction may be used. This vent plug is also installed in the lower part of each section by the partition 7 having the flange portion 54. The vent plug is installed at the lower part of each section by shrinking the vent plug against the biasing force of the biasing member 56 and placing it on the flange portion 54. Further, the vent plug can be removed from below the heat transfer plate by contracting the vent plug against the bias of the biasing member 56. The sliding of the fixing pin 55 and the second ventilation pipe 53 can be performed by hooking the tool pin shown in FIG. 31 on the ring of the fixing pin 55 or the ventilation hole at the bottom of the second ventilation pipe 53.

<Second production method of reaction product>
The second method for producing a reaction product in the present invention is a method for producing a reaction product using the second plate reactor described above, and supplying a heat medium having a desired temperature to the heat transfer tube. And a step of supplying a reaction raw material to a gap between adjacent heat transfer plates filled with a catalyst to obtain a reaction product discharged from the gap. In the first method, the reaction raw material is composed of ethylene; at least one selected from the group consisting of hydrocarbons having 3 and 4 carbon atoms and tertiary butanol, or unsaturated aliphatic aldehydes having 3 and 4 carbon atoms. At least one selected from the group; hydrocarbons having 4 or more carbon atoms; xylene and / or naphthalene; olefins; carbonyl compounds; cumene hydroperoxides; butenes; or ethylbenzenes, and the reaction product is ethylene oxide; At least one of unsaturated aliphatic aldehydes of

number

3 and 4 and unsaturated fatty acids of

number

3 and 4; maleic acid; phthalic acid; paraffin; alcohol; acetone and phenol; butadiene;

The second plate reactor is applied to the process of fixed bed contact reaction, and among these reaction processes, the reaction process may deteriorate the catalyst due to the high reaction heat or the reaction performance may decrease. Applies to In particular, the second plate reactor can be applied to a reaction raw material of a fluid that can flow through a catalyst layer filled with a catalyst such as gas or liquid, but it removes heat compared to a liquid state. It can be suitably used when the gas is difficult.

For example, in the reaction to which the second plate reactor is effectively applied, 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 the number of carbon atoms. At least one selected from the group consisting of 3 and 4 unsaturated aliphatic aldehydes; hydrocarbons having 4 or more carbon atoms such as n-butane and benzene; xylene and / or naphthalene; olefins; carbonyl compounds; cumene hydroperoxide; Butene; or ethylbenzene; and the resulting 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; A reaction that is paraffin; alcohol; acetone and phenol; butadiene; or styrene.

Particularly preferably, the second plate reactor is applied to a gas phase catalytic oxidation reaction, which is known to easily generate hot spots. The reaction raw material is selected from the group consisting of at least one reaction raw material selected from the group consisting of hydrocarbons having 3 and 4 carbon atoms and tertiary butanol, or the group consisting of unsaturated aliphatic aldehydes having 3 and 4 carbon atoms. A reaction that is at least one of the raw materials can be mentioned.

Specifically, the hydrocarbon having 3 carbon atoms includes propylene and propane. Examples of the hydrocarbon having 4 carbon atoms include isobutylene, butenes, and butanes. Examples of the unsaturated aliphatic aldehyde having 3 and 4 carbon atoms include acrolein and methacrolein, and examples of the unsaturated fatty acid having 3 and 4 carbon atoms include acrylic acid and methacrylic acid.

In the second production method of the reaction product, a known catalyst used in a conventional catalytic reaction using the reaction raw material, for example, a catalytic reaction of the reaction raw material using a multi-tubular reactor, is used as the catalyst. be able to. The catalyst may be mixed with inert particles such as mullite balls that are not reactive in the catalytic reaction. In the second production method of the reaction product, the temperature of the heat medium supplied to the heat transfer tube is, for example, the reaction conditions in the conventional contact reaction, for example, the contact reaction of the reaction raw material using a multi-tube reactor. As a reference, it can be obtained from optimization of reaction conditions in the reaction using the second plate reactor. Furthermore, other reaction conditions in the second production method of the reaction product can be obtained by optimization using a known technique, for example, similarly to the temperature of the heat medium described above. Or the reaction conditions of the 1st manufacturing method of the reaction product mentioned above and the 3rd manufacturing method of the reaction product mentioned below are applicable to the reaction conditions in the 2nd manufacturing method of a reaction product.

<Third production method of reaction product>
The third method for producing the reaction product is as follows: (A) a plate reactor having a catalyst layer formed between heat transfer plates, a group consisting of hydrocarbons having 3 and 4 carbon atoms, and tertiary butanol. A reaction raw material mixture containing at least one reaction raw material selected from the group consisting of molecular oxygen and catalytic gas phase oxidation of the reaction raw material, unsaturated hydrocarbons, and unsaturated fats having 3 and 4 carbon atoms At least one reaction product selected from the group consisting of group aldehydes, or (B) a plate reactor equipped with a catalyst layer formed between heat transfer plates, having 3 and 4 carbon atoms. Supplying at least one reaction raw material selected from the group consisting of saturated aliphatic aldehydes and a reaction raw material mixture containing molecular oxygen, catalytic vapor phase oxidation of the reaction raw material, and unsaturated fatty acids having 3 and 4 carbon atoms A method for producing at least one reaction product selected from Ranaru group.

Furthermore, in the third production method of the reaction product, the plate reactor is divided into a plurality of reaction zones having different average layer thicknesses of the catalyst layers, and the plurality of reaction zones are independently provided with temperature. The adjusted heat medium is supplied, the heat generated by the oxidation is removed through the heat transfer plate, and the temperature in the catalyst layer is controlled independently.

Furthermore, in the third production method of the reaction product, the temperature T (S1) of the heat medium supplied to the reaction zone S1 closest to the inlet of the reaction raw material mixture is adjacent to the reaction zone S1, It is higher than the temperature T (S2) of the heating medium supplied to the reaction zone S2 located downstream of the flow of the mixture.

Furthermore, in the third production method of the reaction product, the amount of the reaction material loaded when oxidizing at least one of the reaction materials selected from the group consisting of the hydrocarbons having 3 and 4 carbon atoms and tertiary butanol is oxidized. Is at least 150 liters per hour [converted to the standard state (temperature 0 ° C., 101.325 kPa)] or more, and at least one reaction raw material selected from the group consisting of the above-mentioned unsaturated aliphatic aldehydes having 3 and 4 carbon atoms. When the seed is oxidized, the loading amount of the reaction raw material is 160 liters per hour per liter of the catalyst [standard state (temperature 0 ° C., 101.325 kPa) conversion] or more.

The reaction raw material used in the third production method of the reaction product is at least one reaction raw material selected from the group consisting of hydrocarbons having 3 and 4 carbon atoms and tertiary butanol, or 3 and 4 carbon atoms. It is at least one reaction raw material selected from the group consisting of unsaturated aliphatic aldehydes. Examples of the hydrocarbon having 3 carbon atoms include propylene and propane. Examples of the hydrocarbon having 4 carbon atoms include isobutylene, n-butene, isobutene, n-butane, and isobutane. Examples of the unsaturated aliphatic aldehyde having 3 and 4 carbon atoms include acrolein and methacrolein.

The state of these reaction raw materials is not particularly limited as long as it has fluidity to flow through the catalyst layer, but it can be preferably exemplified as a gas (reaction raw material gas).

Moreover, butadiene is mentioned as an unsaturated hydrocarbon in the unsaturated hydrocarbon which is the reaction product, the unsaturated aliphatic aldehyde having 3 and 4 carbon atoms, and the unsaturated fatty acid having 3 and 4 carbon atoms. Examples of the unsaturated aliphatic aldehyde having 3 and 4 include acrolein and methacrolein, and examples of the unsaturated fatty acid having 3 and 4 carbon atoms include acrylic acid, methacrylic acid, maleic acid, and maleic anhydride.

Here, the reason why the third production method of the reaction product is considered to be applicable to all the above reaction products is as follows.

The reason for this is, for example, the basic composition of the catalyst used in the production of butadiene from acrolein, acrolein of 3 carbon atoms, methacrolein from 4 isobutylene, and normal butene (for example, molybdenum (Mo) -bismuth (Bi)). System), production method, and shape are basically the same, and the reaction type and process in the production of the reaction product are industrially the same. Furthermore, the same basic composition (for example, molybdenum (Mo) -vanadium (V) system), shape is used for unsaturated aliphatic aldehydes such as acrolein to acrylic acid, methacrolein to methacrylic acid, and butenes to maleic anhydride. It is mentioned that the reaction is industrially produced by the same reaction type and process. All of these reactions are catalytic gas phase oxidation with molecular oxygen, and are reactions with a large exotherm, and according to the knowledge of the present inventors, have similar reaction characteristics, and a third production method of a reaction product. Can be applied effectively.

The reaction raw material mixture supplied to the plate reactor includes a reaction raw material, molecular oxygen, and, if necessary, a gas inert to the reaction such as nitrogen and water vapor. The reaction raw material may be composed of only one kind, or a mixture (for example, mixed gas) in which two or more kinds are mixed. The composition of the reaction raw material mixture (for example, reaction mixture gas) is appropriately selected according to the purpose.

The content of the reaction raw material with respect to the reaction raw material mixture is not particularly limited, but the total amount of the reaction raw material is preferably 5 to 13 mol%. Further, the content of the molecular oxygen with respect to the reaction raw material mixture is preferably 1 to 3 times the total amount of the reaction raw materials.

The content of the inert gas with respect to the reaction raw material mixture is a value obtained by removing the total amount of reaction raw materials and the amount of molecular oxygen from the total amount of the reaction raw material mixture. The inert gas may be an inert gas obtained by recirculating exhaust gas discharged from the reaction system.

In the third production method of the reaction product, a known catalyst can be used depending on the purpose. Examples of the composition of the catalyst include a metal oxide containing molybdenum, tungsten, bismuth, or the like, or a metal oxide containing vanadium or the like. The metal oxide powder having this composition is formed into a spherical shape, a pellet shape, or a ring shape, and calcined at a high temperature to be used as a catalyst. The catalyst can be formed in a known shape such as a spherical shape with a diameter of 1 to 15 mm (millimeters), a pellet shape having an equivalent diameter of 1 to 15 mm with a shape other than an ellipse, or a hole in the center of a cylindrical column. An open ring shape having a circle outer diameter of 4 to 10 mm, a circle inner diameter of 1 to 3 mm, and a height of 2 to 10 mm is preferably used. A catalyst having the above-mentioned diameter, equivalent diameter, circular outer diameter and height of 3 to 5 mm is more preferable.

When the reaction raw material is propylene, preferred examples of the metal oxide include compounds represented by the following general formula (1).
Mo (a) Bi (b) Co (c) Ni (d) Fe (e) X (f) Y (g) Z (h) Q (i) Si (j) O (k) (1) )

In the above formula (1), Mo is molybdenum, Bi is bismuth, Co is cobalt, Ni is nickel, Fe is iron, X is at least one element selected from the group consisting of sodium, potassium, rubidium, cesium and thallium, Y Is at least one element selected from the group consisting of boron, phosphorus, arsenic and tungsten, Z is at least one element selected from the group consisting of magnesium, calcium, zinc, cerium and samarium, Q is a halogen element, and Si is silica , O represents oxygen.

In the above formula (1), a, b, c, d, e, f, g, h, i, j and k are Mo, Bi, Co, Ni, Fe, X, Y, Z, Q, Represents the atomic ratio of Si and O, and when molybdenum atom (Mo) is 12, 0.5 ≦ b ≦ 7, 0 ≦ c ≦ 10, 0 ≦ d ≦ 10, 1 ≦ c + d ≦ 10, 0.05 ≦ e ≦ 3, 0.0005 ≦ f ≦ 3, 0 ≦ g ≦ 3, 0 ≦ h ≦ 1, 0 ≦ i ≦ 0.5, 0 ≦ j ≦ 40, and k is a value determined by the oxidation state of each element. is there.

On the other hand, when the reaction raw material is acrolein, the metal oxide is preferably exemplified by a compound represented by the following general formula (2).
Mo (12) V (a) X (b) Cu (c) Y (d) Sb (e) Z (f) Si (g) C (h) O (i) (2)

In the above formula (2), X represents at least one element selected from the group consisting of Nb and W. Y represents at least one element selected from the group consisting of Mg, Ca, Sr, Ba and Zn. Z represents at least one element selected from the group consisting of Fe, Co, Ni, Bi, and Al. However, Mo, V, Nb, Cu, W, Sb, Mg, Ca, Sr, Ba, Zn, Fe, Co, Ni, Bi, Al, Si, C, and O are element symbols.

Moreover, in said formula (2), a, b, c, d, e, f, g, h, and i represent the atomic ratio of each element, 0 <a <= 12 with respect to molybdenum atom (Mo) 12, 0 ≦ b ≦ 12, 0 ≦ c ≦ 12, 0 ≦ d ≦ 8, 0 ≦ e ≦ 500, 0 ≦ f ≦ 500, 0 ≦ g ≦ 500, 0 ≦ h ≦ 500, and i is the value of each component The value is determined by the degree of oxidation of each component excluding C.

In a practical reactor, it is required to increase the processing load of the reaction raw material per unit catalyst and increase the productivity of the target reaction product. However, when the processing load of the reaction raw material per unit catalyst is increased, the heat generated by the reaction is appropriately controlled to prevent hot spots, prevent damage to the catalyst, and the conversion rate of the reaction raw material and the target reaction product Measures are required to improve the yield.

In order to cope with this, the shape of the plate reactor used in the third production method of the reaction product is not particularly limited, but is characterized by the following (1) and (2).
(1) The catalyst layers formed between the heat transfer plates are divided into a plurality of reaction zones having different average layer thicknesses.
(2) A plurality of reaction zones are supplied with temperature-adjusted heat media, and if necessary, supplied with a plurality of independently temperature-adjusted heat media to transfer heat generated by the catalytic gas phase oxidation reaction. Heat is removed across the heat plate, and the temperature in the catalyst layer can be controlled independently.

As such a plate reactor, the plate reactor of the present invention described above can be used. The use of the plate reactor of the present invention in the second method means that in the third method for producing a reaction product, the effect of the plate reactor of the present invention and the effect of the third method of producing a reaction product From the viewpoint of obtaining both effects, it is preferable.

Hereinafter, embodiments of the plate reactor used in the third production method of the reaction product will be described. In the following description, for the sake of convenience, description may be made using “reaction gas” which is an aspect of a reaction fluid, which is a general term for a reaction raw material, a reaction raw material mixture, and a mixture of reaction products generated by the reaction.

As a first aspect of the plate reactor, a heat medium flow in which a catalyst is filled in a space between a pair of heat transfer plates to form a reaction zone, and a heat medium is supplied to the outside of the heat transfer plate. A plate reactor having a channel is mentioned.

The reaction zone of the plate reactor can be divided into a plurality of regions, and the thickness of the catalyst layer filled in each reaction zone can be changed by adjusting the distance between the pair of heat transfer plates. It is. In particular, the catalyst layer thickness in each region of the reaction zone is preferably increased from the inlet to the outlet of the reaction raw material mixture to be supplied. In addition, the outside of the heat transfer plate pair is divided into a plurality of heat medium flow paths, and heat mediums having different temperatures can be supplied to the flow paths.

The direction of the reaction gas supplied to the plate reactor flows along the heat transfer plate, and the heat medium is supplied to the outside of the pair of heat transfer plates. The flow direction of the heat medium is not particularly limited, but an industrial scale reaction apparatus usually needs to accommodate a large amount of catalyst, and a large number of heat transfer plate pairs are installed. A direction perpendicular to the flow is convenient.

The reaction amount in the normal reaction is the largest at the inlet portion of the reaction gas, the generation of reaction heat accompanying the reaction is the largest, and decreases in the direction of the reaction gas outlet. By adjusting the distance between the heat transfer plates and changing the average layer thickness of the catalyst layer, the reaction and the heat generated by the reaction can be controlled more precisely, preventing hot spots as the catalyst layer temperature rises, and damaging the catalyst. Can be prevented.

In addition, by using the above plate reactor, an increase in the pressure loss of the reaction gas under the condition that the processing load per unit catalyst of the reaction gas is high as seen in the multi-tube reactor, and accompanying this It is possible to eliminate the decrease in the yield of the target reaction product. Furthermore, the energy cost of the compressor for supplying the reaction gas and the like accompanying the increase in the reactor internal pressure can be reduced.

FIG. 41 shows a first specific example of the plate reactor.
A thin heat transfer plate (57) that separates the heat medium flow path (60-1, 60-2, and 60-3) and the catalyst layer (43) is provided from the reaction gas inlet (58) to the outlet (59). In order to change the thickness of the catalyst layer (43) along the flow, it is deformed. Here, the average layer thickness of the catalyst layer is a distance between the plates measured in a direction perpendicular to the flow direction of the reaction gas.

The thickness of the catalyst layer (43) formed between the pair of heat transfer plates (57) corresponds to each heat medium flow path (60-1, 60-2, and 60-3), and the reaction Bands (S1, S2, and S3) are formed. (61) is a heat medium supply port. In the above, there are three reaction zones, but this is an example, and the number of reaction zones is not limited.

Further, the heat transfer plate (57) can be a flat plate, an embossed one having irregularities, or a corrugated plate formed in a direction perpendicular to the flow of the reaction gas. In consideration of the heat transfer efficiency between the reaction gas and the heat medium, an uneven plate or corrugated plate shape is preferably used. Here, in the first specific example, the average layer thickness of the catalyst layer when embossing or corrugated plate was used for the heat transfer plate (57) was defined by the following equation.
(Formula) [Average thickness of catalyst layer] = [Volume of catalyst layer] / [Length (width) of heat transfer plate (length perpendicular to the paper surface in FIG. 41)] / [Reaction of heat transfer plate] Gas flow direction length]

Here, the [volume of the catalyst layer] refers to a pair of heat transfer plates in which a pair of heat transfer plates on which the catalyst layer is formed are kept perpendicular to the ground and a lid is placed on the bottom (the bottom surface of each reaction zone). When a liquid such as water or glass beads having a diameter of 1 mm or less is poured into a space sandwiched between heat plates, the volume of the liquid such as water or glass beads having a diameter of 1 mm or less necessary to fill the space is set. .

As a second aspect of the plate reactor, two corrugated plates shaped into a continuous pattern having a main part of an arc, an elliptical arc, a rectangle or a polygon are faced to each other. A plurality of heat transfer plates in which the convex portions of the plates are joined to each other to form a plurality of heat transfer channels are arranged, and the corrugated convex portions and concave portions of adjacent heat transfer plates face each other at a predetermined interval. And a plate reactor in which the catalyst layer is formed. Here, the above-mentioned “corrugated sheet shaped into a continuous pattern having a circular arc, elliptical arc, rectangle or polygon as a main component” means that the wave shape of the corrugated sheet is an arc, elliptical arc, rectangular or multiple It means that the pattern is a continuous pattern (shape) with a part of a square as a main component.

In the plate reactor, by changing the shape of a part of the arc, elliptical arc, rectangle, or polygon formed on the corrugated plate, the catalyst layer is moved from the inlet to the outlet of the reaction gas supplied to the catalyst layer. It is possible to change the thickness. The plate reactor can divide the reaction zone into a plurality of regions, and the reaction zone divided into the plurality of regions can correspond to the change in the thickness of the catalyst layer. . Further, a plurality of the divided reaction zones are supplied with a heat medium whose temperature is independently adjusted, and the heat generated by the catalytic gas phase oxidation reaction is removed through the heat transfer plate, so that the temperature in the catalyst layer is reduced. It can be controlled independently.

The direction of the reaction gas supplied to the plate reactor flows along the outside of the heat transfer plate, and the heat medium is supplied inside the pair of heat transfer plates. The flow direction of the heat medium flows in a direction perpendicular to the flow of the reaction gas, that is, a cross flow direction.

The reaction amount in the normal reaction is the largest at the inlet portion of the reaction gas, the generation of reaction heat accompanying the reaction is the largest, and decreases in the direction of the reaction gas outlet. In order to efficiently remove the reaction heat, the corrugated shape of the corrugated plate used for one heat transfer plate and the adjacent heat transfer plate is changed, and the gap between the heat transfer plates is adjusted to adjust the catalyst layer. It is preferable to change the average layer thickness. By changing the average layer thickness of the catalyst layer, the reaction can be controlled more precisely, hot spots accompanying the increase in the catalyst layer temperature can be prevented, and damage to the catalyst can be prevented.

FIG. 42 shows a second specific example of the plate reactor.
As shown in FIG. 42, in the heat transfer plate (57), two thin plates are deformed into a continuous pattern having a circular, elliptical, rectangular or polygonal part as a main component, and are in opposite directions. Facing each other (in a mirror image relationship) to form heat medium flow paths (60-1, 60-2, 60-3). In addition, the pair of heat transfer plates (57) are opposed to each other by a distance corresponding to half of the heat medium flow path to form a gap, and the formed gap is filled with a catalyst to form a catalyst layer (43). . Further, the pair of heat transfer plates (57) includes a reaction gas inlet (58) for introducing the reaction mixed gas into the catalyst layer (43) and a reaction gas outlet (59) for deriving the reaction gas.

The heat medium flow paths have different cross-sectional shapes (cross-sectional areas), and the width of the heat medium flow path (60-1) is the largest. When the width of the heat medium flow path (60-1) is the largest, the interval between the adjacent heat transfer plates (57) is constant, so that the corrugated convex surface portion and the concave surface portion of the adjacent heat transfer plates face each other. The distance (A) formed in this way (that is, the layer thickness of the catalyst layer (43)) is the narrowest. The width of the heat medium flow path gradually decreases from the heat medium flow path (60-2) to (60-3), and the thickness of the catalyst layer (43) corresponding to the heat medium flow path increases. Therefore, the catalyst layers (43) corresponding to the heat medium flow paths (60-1, 60-2, and 60-3) have different average layer thicknesses of the catalyst layers and different average layer thicknesses of the catalyst layers. Multiple reaction zones (S1, S2, and S3) can be formed.

Here, the average layer thickness of the catalyst layer is the average value of the distance (A) measured in the direction perpendicular to the flow direction of the reaction gas in each catalyst layer of each reaction zone (S1, S2, and S3). means. In the second specific example, it is defined using the following calculation formula.
(Expression) [Average thickness of catalyst layer] = [Volume of catalyst layer] / [Length (width) of heat transfer plate (length perpendicular to the paper surface in FIG. 42)] / [Reaction of heat transfer plate] Gas flow direction length]

In the above, there are three reaction zones. However, this is merely an example, and the number of reaction zones is not limited in the third method for producing a reaction product.

43, the configuration of the heat transfer plate (57) used in the second specific example of the plate reactor will be described in more detail. FIG. 43 shows two corrugated sheets deformed into a continuous pattern having a main part of an arc, an elliptical arc, a rectangle or a polygon, and the convex portions of the corrugated sheets are joined to each other. The heat-transfer plate in which the several heat carrier flow path was formed is shown.

The size of the heat medium flow path and the average layer thickness of the catalyst layer are defined by the wave period (L) and the wave height (H) of the corrugated plate. At this time, the wave period (L) is preferably 10 to 100 mm, and more preferably 20 to 50 mm. On the other hand, the height (H) is preferably 5 to 50 mm, and more preferably 10 to 30 mm.

A pair of the heat transfer plates are parallel to each other and are shifted from each other by a distance (L / 2) corresponding to half of the heat medium flow path to form a gap, and the gap is filled with a catalyst to form a catalyst layer.

The thickness of the catalyst layer is adjusted by changing the interval (P) between the pair of parallel heat transfer plates and the period (L) and height (H) of the heat medium flow path. The distance P between the pair of heat transfer plates is usually 10 to 50 mm, and more preferably 20 to 50 mm.

In FIG. 43, the shape of the heat transfer plate is drawn as a part of an arc, but the shape may be a continuous pattern whose main component is an elliptical arc, a rectangle, a triangle, or a part of a polygon. The catalyst layer thickness can be accurately controlled by changing the period (L) and the height (H). The catalyst layer thickness is preferably uniform in the length (width) direction (direction perpendicular to the paper surface) of the heat transfer plate.

Further, the average layer thickness of the catalyst layer correlates with the interval (x) shown in FIG. 43, and the interval (x) is usually 0.7 to 0.00 mm of the average layer thickness of the catalyst layer defined by the above formula. 9 times.

The thickness of the thin plate of the heat transfer plate (57) of each reactor is 2 mm or less, preferably 1 mm or less.

The length of the heat transfer plate (57) in the reaction gas flow direction is 0.5 to 10 m (meters), preferably 0.5 to 5 m, and 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 length in the direction perpendicular to the flow direction of the reaction gas (in FIGS. 41 and 42, the depth perpendicular to the paper surface) is not particularly limited, and is usually 0.1 to 20 m, preferably 3 to 15 m. More preferably, it is 6 to 10 m. The heat transfer plates (57) are stacked in the same manner as in the arrangement shown in FIG. 43, and the number of stacked layers is not limited. In practice, it is determined from the amount of catalyst required for the reaction, but it is from several tens to several hundreds.

The average layer thickness of the catalyst layer in each reaction zone is not particularly limited, but is preferably 4 to 50 mm. The average layer thickness of the catalyst layer in each reaction zone also varies depending on the amount of reaction raw material loaded and the catalyst shape (particle size, etc.), but in the plate reactor shown in FIG. 41, the reaction zone (S1 ) Of the catalyst layer is 4 to 18 mm (more preferably 5 to 13 mm), and the average layer thickness of the catalyst layer in the reaction zone (S2) following the reaction zone (S1) is 5 to 23 mm ( More preferably, the average thickness of the catalyst layer in the reaction zone (S3) following the reaction zone (S2) is 8 to 27 mm (more preferably 10 to 22 mm). .

On the other hand, in the plate reactor shown in FIG. 42, the average layer thickness of the catalyst layer in the reaction zone (S1) is 5 to 20 mm (more preferably 7 to 15 mm), and the reaction following the reaction zone (S1). The average layer thickness of the catalyst layer in the zone (S2) is 7 to 25 mm (more preferably 10 to 20 mm), and the average layer thickness of the catalyst layer in the reaction zone (S3) following the reaction zone (S2) is 12 mm. It can be preferably exemplified that it is ˜30 mm (more preferably 15 to 25 mm).

In addition, it is preferable that the average layer thickness of the catalyst layers in the plurality of reaction zones increases sequentially as it is positioned in the direction from the inlet to the outlet of the reaction gas.

In particular, when oxidizing at least one reaction raw material selected from the group consisting of hydrocarbons having 3 and 4 carbon atoms and tertiary butanol, the loading amount of the reaction raw material is 150 liters per hour per liter of catalyst [standard state (Temperature 0 ° C., 101.325 kPa) conversion] and / or reaction when oxidizing at least one reaction raw material selected from the group consisting of unsaturated aliphatic aldehydes having 3 and 4 carbon atoms When the load of the raw material is 160 liters per hour per liter of the catalyst [converted to a standard state (temperature 0 ° C., 101.325 kPa)] or more, a reaction gas inlet (introducing a reaction gas mixture into the catalyst layer (43)) ( 58) The average layer thickness of the catalyst layer in the reaction zone (S1) connected to 58) is 5 to 15 mm (particularly preferably 7 to 12 mm). The average layer thickness of the catalyst layer in the reaction zone (S2) following the reaction zone (S2) is 7 to 17 mm (particularly preferably 10 to 15 mm), and the average layer of the catalyst layer in the reaction zone (S3) following the reaction zone (S2) More preferably, the thickness is 12 to 27 mm (particularly preferably 15 to 20 mm).

When the average layer thickness of the catalyst layer is smaller than the above range, when the catalyst is filled into the reaction zone S1, it may be difficult to cause the catalyst particles to bridge in the catalyst layer and to increase the filling time. is there. Of course, the minimum layer thickness of the catalyst layer must be larger than the particle size of the catalyst particles. Usually, the minimum thickness of the catalyst layer is preferably 1.5 times or more the catalyst particle size. Therefore, the average layer thickness of the catalyst layer in the above example is suitable when the particle size of the catalyst particles is 3 to 5 mm.

On the other hand, when the average layer thickness of the catalyst layer is larger than the above range, hot spots are likely to occur. In particular, a reaction zone near the outlet of the reaction gas, for example, a situation in which the temperature in the catalyst layer of the reaction zone (S3) rises and a hot spot phenomenon occurs, or hot where the conversion rate of the reaction raw material becomes too high than the optimum value. If the situation is close to the spot, the reaction results may be reduced, and the yield of the target reaction product may be reduced. When the above situation deteriorates and a hot spot is generated, the catalyst may be damaged. At this time, it is necessary to limit the reaction amount by lowering the temperature of the heat medium to promote the removal of reaction heat, or to reduce the supply amount of the reaction mixed gas and reduce the load of the reaction raw material.

The details of the average layer thickness of the catalyst layer vary depending on the amount of reaction, but it may be continuously changed from the inlet to the outlet of the catalyst layer (43) or may be changed stepwise. Rather, considering the unevenness of the reaction activity during the production of the catalyst, the degree of freedom may be secured by changing the average layer thickness of the catalyst layer in stages.

Further, the number of divisions of the reaction zone is preferably 2 to 5, and the average layer thickness of the catalyst layer in each reaction zone is preferably increased from the inlet to the outlet of the reaction gas.

Furthermore, the length of the reaction gas flow direction of the catalyst layer in each reaction zone is determined in consideration of the conversion rate of the reaction raw material, etc., for example, when the reaction zone is divided into three, The catalyst layer length is 10% to 55% for the reaction zone (S1), 20% to 65% for the reaction zone (S2), and 25% to 70% for the reaction zone (S3) with respect to the catalyst layer length. It is preferable to apply. Moreover, it is preferable to change the catalyst layer length of the reaction zone (S3) portion according to the achievement of the conversion rate of the reaction raw material.

As mentioned above, in a practical reactor, even when the processing load of the reaction raw material per unit catalyst is increased, the heat generated by the reaction is appropriately controlled to prevent hot spots and prevent damage to the catalyst. In addition, it is necessary to improve the conversion rate of the reaction raw materials and the yield of the target reaction product.

In the third production method of the reaction product, the amount of reaction raw material when oxidizing at least one of the reaction raw materials selected from the group consisting of hydrocarbons having 3 and 4 carbon atoms and tertiary butanol, 150 liters per hour per liter of catalyst [standard state (temperature 0 ° C., 101.325 kPa) conversion] or more. When oxidizing at least one of the reaction raw materials selected from the group consisting of the above hydrocarbons having 3 and 4 carbon atoms and tertiary butanol, the loading amount of the reaction raw materials is 170 to 290 liters per liter of catalyst [standard] The state (converted at a temperature of 0 ° C. and 101.325 kPa) is preferable, and the conversion rate is particularly preferably 200 to 250 liters per hour per liter of catalyst [converted to a standard state (converted at a temperature of 0 ° C. and 101.325 kPa)]. More than 150 liters per hour [converted to the standard state (temperature 0 ° C., 101.325 kPa)] per 1 liter of catalyst means that the reaction raw material load is higher than the reaction raw material processing load per unit catalyst. To do.

In addition, when oxidizing at least one of the reaction raw materials selected from the group consisting of unsaturated aliphatic aldehydes having 3 and 4 carbon atoms, the loading amount of the reaction raw materials is 160 liters per hour [standard state (temperature 0 ° C., 101.325 kPa) conversion] or more. When oxidizing at least one reaction raw material selected from the group consisting of the above-mentioned unsaturated aliphatic aldehydes having 3 and 4 carbon atoms, the loading amount of the reaction raw material is 180 to 300 liters per liter of catalyst [standard state ( The temperature is preferably 0 ° C. and 101.325 kPa), and particularly preferably 200 to 250 liters per hour per 1 liter of catalyst [standard state (temperature 0 ° C., 101.325 kPa) equivalent]. More than 160 liters per hour [converted to the standard state (temperature 0 ° C., 101.325 kPa)] per liter of catalyst means that the reaction raw material is loaded with a higher processing load of the reaction raw material per unit catalyst. To do.

In the third production method of the reaction product, the temperature of the heat medium supplied to the plurality of reaction zones is controlled independently in order to improve the conversion rate of the reaction raw material and the yield of the target reaction product. In the third method for producing a reaction product, the temperature unit is the degree of Celsius [° C.].

In the third production method of the reaction product, the temperature T (S1) of the heat medium supplied to the reaction zone S1 closest to the inlet of the reaction raw material mixture is adjacent to the reaction zone S1, and the flow of the reaction raw material mixture A temperature higher than the temperature T (S2) of the heat medium supplied to the reaction zone S2 located downstream is important for improving the conversion rate of the reaction raw material and the yield of the target reaction product.

Further, “T (S1) -T (S2)” is more preferably 5 ° C. or more, further preferably 10 ° C. or more, and particularly preferably 15 ° C. or more. “T (S1) -T (S2)” is preferably 40 ° C. or lower.

The temperature of the heat medium supplied to the reaction zone located downstream of the flow of the reaction raw material mixture in the reaction zone S2 is arbitrary and may be the same as or different from the temperature T (S2). Good. However, a temperature lower than the temperature T (S2) is preferred particularly in a reaction zone including a region where the conversion rate of the reaction raw material is 90% or more.

41 and 42, the temperature T (S1) of the heat medium supplied to the reaction zone (S1) is equal to the temperature T of the heat medium supplied to the reaction zone (S2). When higher than (S2), it is possible to improve the conversion rate of the reaction raw material and the yield of the target reaction product.

The temperature of the heat medium supplied to the reaction zone closest to the outlet of the reaction raw material mixture is the temperature of the heat medium supplied to the reaction zone adjacent to the reaction zone and upstream of the flow of the reaction raw material mixture. A lower value is preferable in order to further improve the yield of the target reaction product. The absolute value of the temperature difference is more preferably 5 ° C. or higher, and particularly preferably 10 ° C. or higher. In addition, it is preferable that the absolute value of this temperature difference is 30 degrees C or less.

In the third production method of the reaction product, T (Sj) is the temperature of the heat medium supplied to any unspecified reaction zone S (j), and the reaction raw material mixture is adjacent to the reaction zone S (j). When the temperature of the heat medium supplied to the reaction zone S (j + 1) located downstream of the flow is T (Sj + 1), the T (Sj) and the T (Sj + 1) are T (Sj)> T ( It is more preferable to satisfy the relationship of Sj + 1).

In the example of the plate reactor described in FIGS. 41 and 42, the temperature of the heat medium supplied to the reaction zone (S1) is T (S1), and the temperature of the heat medium supplied to the reaction zone (S2) is It is preferable to satisfy the relationship of T (S1)> T (S2)> T (S3), where T (S2) and the temperature of the heat medium supplied to the reaction zone (S3) are T (S3). It will be.

In the third production method of the reaction product, T (Sj) is the temperature of the heat medium supplied to any unspecified reaction zone S (j), and the reaction raw material mixture is adjacent to the reaction zone S (j). T (Sj) and T (Sj + 1) are T (Sj) −, where T (Sj + 1) is the temperature of the heat medium supplied to the reaction zone S (j + 1) located downstream of the flow of It is more preferable to satisfy the relationship of T (Sj + 1) ≧ 5 in order to further improve the yield of the target reaction product. Furthermore, T (Sj) −T (Sj + 1) ≧ 10 is more preferable, and T (Sj) −T (Sj + 1) ≧ 15 is particularly preferable. Note that the value of T (Sj) −T (Sj + 1) is preferably 30 or less.

As described above, the temperature of the heat medium is adjusted in order to keep the conversion rate of the reaction raw material optimal. In the third production method of the reaction product, when it is desired to promote the progress of the reaction and improve the conversion rate of the reaction raw material, the heat medium supplied to the reaction zone located upstream in the flow direction of the reaction raw material mixture Adjust the reaction by raising the temperature. Conversely, when it is desired to lower the over-conversion rate, first, the reaction conversion rate is adjusted by lowering the temperature of the heat medium supplied to the reaction zone located downstream in the flow direction of the reaction raw material mixture.

In the third production method of the reaction product, the conversion rate of the reaction raw material at the reaction product outlet of the plate reactor is preferably 90% or more, more preferably 95% or more, and particularly preferably. 97% or more.

The heat medium is supplied to each of the reaction zones at an optimum temperature. At this time, the direction in which the heat medium flows is preferably orthogonal to the flow direction of the reaction gas.

Also, the temperature difference between the inlet temperature and the outlet temperature of the heat medium is preferably 0.5 to 10 ° C, more preferably 2 to 5 ° C.

In the case of the plate reactor shown in FIG. 42, in each of the heat medium flow paths (60-1, 60-2, 60-3), the flow rate of the heat medium, temperature, and It is also possible to change the flow direction. Further, even in one reaction zone, the heat medium having the same temperature may flow independently in the same direction or flow in the opposite direction for each of one to a plurality of flow paths. It is also possible to supply the heat medium supplied to and discharged from the heat medium flow path in a certain reaction zone to the heat medium flow path in the same or another reaction zone.

The heat generated by the reaction is removed through the heat transfer plate, and the temperature in the catalyst layer in the reaction zone is more reliably and independently controlled, so that the temperature of the heat medium supplied to the reaction zone is stable. It is important to control the temperature of the heat medium, and it is preferable that the temperature of the heat medium has independent temperature control means. For example, when the heat medium from the reaction zone S (j + 1) is recirculated to the upstream reaction zone S (j), after adjusting the heat medium temperature T (Sj) by the temperature control means, the reaction zone S (j) It is preferable to supply to. It is also possible to adjust the temperature after joining or branching with a heat medium from another reaction zone or a heat medium having a different temperature, and supplying it to the reaction zone S (j).

The temperature of the heat medium supplied to the heat medium flow path is preferably 200 to 600 ° C. When the reaction raw material is at least one of the reaction raw materials selected from the group consisting of hydrocarbons having 3 and 4 carbon atoms and tertiary butanol, it is preferably supplied to each reaction zone at 250 to 450 ° C. Preferably, it is 300 to 420 ° C. 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 more preferably 320 to 400 ° C.

On the other hand, when the reaction raw material is at least one reaction raw material selected from the group consisting of unsaturated aliphatic aldehydes having 3 and 4 carbon atoms, it is preferably supplied to each reaction zone at 200 to 350 ° C. Preferably, it is 250 to 330 ° C. When the reaction raw material is acrolein, the temperature of the heat medium supplied to the plurality of reaction zones is preferably 250 to 320 ° C.

In the same reaction zone, it is preferable that the temperature of the heat medium is basically the same, but it is possible to change the temperature within a range where the hot spot phenomenon does not occur.

The flow rate of the heat medium supplied to the heat medium flow path is determined from the reaction heat amount and the heat transfer resistance. However, the heat transfer resistance is less likely to cause a problem because the gas side of the reaction gas is usually larger than the liquid heat medium, but the liquid linear velocity in the heat medium flow path is preferably 0.3 m / s or more. Adopted. In order to make the resistance on the heat medium side small and not cause a problem compared to the reaction gas side heat transfer resistance, 0.5 to 1.0 m / s is most suitable. If it is too large, the power of the circulation pump of the heat medium becomes large, which is not preferable in terms of economy. In addition, the heat medium used can use a well-known thing.

In the third production method of the reaction product, the reaction pressure is usually atmospheric pressure to 3,000 kPa (kilopascal), preferably atmospheric pressure to 1,000 kPa (kilopascal), more preferably atmospheric pressure to 300 kPa. .

Next, although it demonstrates concretely using an Example, this invention is not limited to an Example at all.

Example 1
Since the first plate reactor can efficiently transfer heat in the catalyst layer, it can be applied to any raw material, catalyst, and reaction as long as the reaction requires heat transfer. Here, a reaction for producing acrolein and acrylic acid by oxidizing propylene with oxygen is shown as an example.

In the production of acrolein by oxidizing propylene with molecular oxygen, the catalyst is disclosed in JP-A 63-54942, JP-B 6-13096, JP-B 6-38918, etc. According to the disclosed method, it was produced as follows.

(Manufacture of catalyst)
94 parts by weight of paramolybdate ammon was heated and dissolved in 400 parts by weight of pure water. On the other hand, 7.2 parts by weight of ferric nitrate, 25 parts by weight of cobalt nitrate and 38 parts by weight of nickel nitrate were dissolved by heating in 60 parts by weight of pure water. These solutions were mixed with sufficient stirring to obtain a slurry-like solution.

Next, 0.85 parts by weight of borax and 0.36 parts by weight of potassium nitrate were dissolved in 40 parts by weight of pure water under heating and added to the slurry. Next, 64 parts by weight of granular silica was added and stirred. Next, 58 parts by weight of bismuth carbonate mixed with 0.8% by weight of Mg in advance was added and mixed by stirring. After the slurry was heated and dried, it was heat-treated at 300 ° C. for 1 hour in an air atmosphere. Using a molding machine, tablets were molded into tablets having a diameter of 4 mm and a height of 3 mm, and then calcined at 500 ° C. for 4 hours to obtain catalyst A.

The obtained catalyst A has Mo (12) Bi (5) Ni (3) Co (2) Fe (0.4) Na (0.2) Mg (0.4) B (0.2) K (0 .1) A composite oxide having a composition ratio of Si (24) O (x) (the oxygen composition x is a value determined by the oxidation state of each metal).

The oxidation reaction of propylene was performed using a plate reactor A having the same configuration as the plate reactor of FIG. The plate reactor A has a heat transfer plate formed by forming a stainless steel plate having a thickness of 1 mm and joining two of the formed plates, and the long diameter (L) of the heat transfer tube 1 is 40 mm. The short diameter (H) of the heat transfer tube is 20 mm, the distance (P) between the axes of the heat transfer plate is 26 mm, has one reaction zone, and accommodates the catalyst A. When the shape of the molded plate was measured with a CCD laser displacement meter (manufactured by Keyence Co., Ltd., LK-G152), the error relative to the design value of the molded plate was less than ± 0.2 mm. In the plate reactor A, the heat transfer plate is arranged so that its axis is in the vertical direction.

The design value of the distance between the surfaces of the heat transfer plates in the plate reactor A is the distance between the convex edge by the heat transfer tube of one heat transfer plate and the concave edge by the connection portion of the heat transfer tube of the other heat transfer plate. 15 mm. When the distance between the surfaces of the heat transfer plates was measured in 7 places along the axial direction of the heat transfer plates and 3 places along the axial direction of the heat transfer tubes in the heat transfer plate, a total of 21 points were measured. The difference between the design value and the actual measurement value was 17 mm or less at 17 points. In addition, the distance between the surfaces of the heat transfer plate was set at a position of 30 mm from the tip of a bar member having a length of 50 cm and a diameter of 4 mm, and a measuring bar member having a diameter of 1 mm, lengths of 15.2 mm and 14.8 mm was attached at a right angle. Two types of measurement fittings were inserted into the gaps between the heat transfer plates and measured. In the plate reactor A, the difference between the measured values with respect to the design value in the distance between the surfaces of the heat transfer plates is 0 mm.

A molten nitrate salt (nighter) was used as the heating medium. The heat medium was adjusted to a temperature corresponding to the reaction zone and supplied to the heat transfer tube. The heating medium was supplied so that the flow rate of the heating medium was 0.7 m or more per second.

As a raw material gas, a reaction raw material mixed gas having a propylene concentration of 9.5 mol%, a water concentration of 9.5 mol%, an oxygen concentration of 14.2 mol%, and nitrogen of 66.8% at a rate of 6750 liters per hour (standard state) Then, the pressure was supplied to the plate reactor so that the pressure at the inlet of the reactor became 0.07 MPaG (megapascal gauge).

Table 1 shows the major axis and minor axis of the heat transfer tube in the plate reactor A, the length of the reaction zone, and the distance (P) between the heat transfer plates. The temperature of the heat medium, the conversion rate of propylene (PP) as a raw material, the selectivity obtained by dividing the total yield of acrolein (ACR) and acrylic acid (AA) as target products by the conversion rate of propylene (PP), Table 2 shows the peak temperature of the catalyst layer.

(Example 2)
First, the reaction was carried out under the same conditions as in Example 1, using a plate reactor B having the same structure as the plate reactor A except that the distance (P) between the axes of the heat transfer plate was 26.5 mm. Carried out. The measured value of the distance between the surfaces of the heat transfer plates in the plate reactor B is the distance between the convex edge of one heat transfer plate and the concave edge of the other heat transfer plate, as in Example 1. The distance was measured and found to be 15.5 ± 0.2 mm at 16 points, which is 76% of the measurement points. The plate reactor B corresponds to the case where the difference between the measured values with respect to the design value is +0.5 mm. In this reaction, the peak temperature of the catalyst layer reached 419 ° C. and further increased, so the reaction was once stopped.

The reaction was carried out in the same manner as in Example 1 except that the temperature of the heating medium was lowered to 338 ° C. so that the peak temperature of the catalyst layer in the plate reactor B was the same as the peak temperature of the catalyst layer in Example 1. As a result, as shown in Table 2, reaction results equivalent to those of Example 1 were obtained.

(Example 3)
First, the reaction was carried out under the same conditions as in Example 1, using a plate reactor C having the same structure as the plate reactor A except that the distance (P) between the axes of the heat transfer plates was 27.5 mm. Carried out. The measured value of the distance between the surfaces of the heat transfer plates in the plate reactor C is the distance between the convex edge of one heat transfer plate and the concave edge of the other heat transfer plate, as in Example 1. When the distance was measured, it was 16 at 18 points which is 86% of the measurement points. It was 5 ± 0.2 mm. The plate type reactor C corresponds to the case where the difference between the measured value and the design value is +1.5 mm. In this reaction, the peak temperature of the catalyst layer reached 442 ° C. and further increased, so the reaction was once stopped.

The reaction was carried out in the same manner as in Example 1 except that the temperature of the heating medium was lowered to 330 ° C. so that the peak temperature of the catalyst layer in the plate reactor C was the same as the peak temperature of the catalyst layer in Example 1. As a result, as shown in Table 2, reaction results equivalent to those of Example 1 were obtained.

(Comparative Example 1)
First, the reaction was performed under the same conditions as in Example 3 using a plate reactor D having the same structure as the plate reactor A except that the distance (P) between the axes of the heat transfer plates was 28.5 mm. Carried out. The measured value of the distance between the surfaces of the heat transfer plates in the plate reactor D is the distance between the convex edge of one heat transfer plate and the concave edge of the other heat transfer plate, as in Example 1. When the distance was measured, 17 points were obtained at 19 points which were 90% of the measurement points. It was 5 ± 0.2 mm. The plate reactor D corresponds to the case where the difference between the measured values with respect to the design value is +2.5 mm. In this reaction, the peak temperature of the catalyst layer exceeded 450 ° C., and since the runaway reaction might occur, the reaction was once stopped. The reaction was carried out in the same manner as in Example 1 except that the temperature of the heat medium was lowered to 300 ° C. However, the conversion did not exceed 50% and the reaction did not proceed.

Example 4
Propylene oxidation was performed using a plate reactor E having two reaction zones. In the plate reactor E, the first reaction zone has the same structure as the plate reactor B. The second reaction zone following the first reaction zone is a plate in which the short diameter (H) of the heat transfer tube is 16 mm, the length of the reaction zone is 400 mm, and the distance between the axes of the heat transfer plate is 27.5 mm It has the same structure as the type reactor.

In the first reaction zone in the plate reactor E, the design value of the distance between the surfaces of the heat transfer plates is the distance between the convex edge of one heat transfer plate and the concave edge of the other heat transfer plate. It was 5 mm. The first reaction zone corresponds to a case where the difference between the measured values with respect to the average value is +0.5 mm in the distance between the surfaces of the heat transfer plates. In the second reaction zone in the plate reactor E, the design value of the distance between the surfaces of the heat transfer plates is 18 as the distance between the convex edge of one heat transfer plate and the concave edge of the other heat transfer plate. 0.5 mm. Moreover, when the said distance was measured similarly to Example 1, the measured value was 18.5 +/- 0.2mm in 13 places which are 87% of a measurement point. The second reaction zone corresponds to a case where the difference between the measured values with respect to the average value is +1.5 mm in the distance between the surfaces of the heat transfer plates.

In each reaction zone, the temperature of the heating medium in the first reaction zone was set to 330 ° C. so that the peak temperature of the catalyst layer was the same as the peak temperature of the catalyst layer in Example 1, and the heating medium in the second reaction zone was The reaction was carried out under the same conditions as in Example 1 except that the temperature was 328 ° C. As a result, as shown in Table 2, excellent reaction results were obtained in the same manner as in Example 1.

(Comparative Example 2)
Propylene oxidation was performed using a plate reactor F having two reaction zones. In the plate reactor F, the first reaction zone has the same structure as the plate reactor D, and the second reaction zone is the same as the second reaction zone in Example 4. The first reaction zone in the plate reactor F corresponds to the case where the difference between the measured values with respect to the design value is +2.5 mm, and the second reaction zone in the plate reactor F is the same as in Example 4. This corresponds to the case where the difference between the measured value and the design value is +1.5 mm.

The reaction was carried out under the same conditions as in Example 1 except that the temperature of the heating medium was the same as in Example 4. As a result, the peak temperature of the catalyst layer exceeded 450 ° C., and a runaway reaction might occur. The reaction was once stopped. The reaction was carried out in the same manner as in Example 1 except that the temperature of the heat medium in the first reaction zone was lowered to 300 ° C., but the conversion did not exceed 50% and the reaction did not proceed.

(Example 5)
A plate reactor shown in FIG. 16 was manufactured for a filling test. Six heat transfer plates were installed. The length in the axial direction of the heat transfer tube in the heat transfer plate (the width of the heat transfer plate) is 5 m. A locking member for a ventilation plate (perforated plate) was installed below the heat transfer plate. The height of the heat transfer plate in the axial direction of the heat transfer plate from the vent plate is 1.88 m, and a straight portion without the heat transfer tube is formed 150 mm upward from the vent plate. Partitions are installed at 50 cm intervals. The partition was of the shape shown in FIG. 17, and the plate thickness was 5 mm.

The heat transfer plate is formed by molding a stainless steel (SUS304L) steel plate having a thickness of 1 mm so that the cross-sectional shape thereof is a shape in which an arcuate recess and a protruding edge formed between the recesses are continuous. It was manufactured by welding the protruding edges of two steel plates. The specifications of the heat transfer tube in this heat transfer plate are shown in Table 3 below. In the plate reactor, the distance between the straight portions in adjacent heat transfer plates was 24 mm.

In the plate reactor, a catalyst was packed in a compartment formed by adjacent heat transfer plates and partitions. The catalyst includes Mo (12) Bi (5) Co (3) Ni (2) Fe (0.4) Na (0.4) B (0.2) K (0.08) Si (24) O ( A composite metal oxide powder having the composition x) was prepared, molded, molded into a cylindrical shape having an outer diameter of 4 mmφ and a height of 3 mm, and baked. Here, Mo, Bi, Co, Ni, Fe, Na, B, K, Si, and O are atomic symbols, and (x) of O (x) is a value determined by the oxidation state of each metal oxide.

For the catalyst filling, a vibrating feeder having the same width as the partition interval of 50 cm was used. The catalyst was supplied to the compartment at a filling rate of 1 L (liter) / min or less (about 0.8 to 0.9 L / min). More specifically, 11.6 liters of the catalyst was weighed and 33 bags each divided into plastic bags were prepared, and each compartment was filled with the vibration feeder. The calculated theoretical value of the filling height obtained from the volume of each compartment is 182.5 cm.

Thereafter, in order to measure the height of the packed bed, the upper surface of the formed catalyst layer is leveled, the distance from the upper end of the heat transfer plate is measured, and the distance between the distance and the height of the heat transfer plate from the vent plate is measured. The filling height was determined from the difference. This distance was measured at 11 points at intervals of 5 cm in one section. There was a variation in the catalyst supply speed by the vibration feeder, and the supply speed sometimes increased temporarily. When the supply speed fluctuates extremely, the catalyst layer height increases, sometimes bridging occurs, and sometimes overflows from the section between the heat transfer plates, but at that time, the locking member attached to the lower part of the section , The vent plate was removed, the catalyst was extracted and refilled. It was sufficient to carry out refilling three times in total, out of a total of 300 filling operations.

From the measurement result of the packed bed height, the height of the catalyst layer was within ± 5 cm from the theoretical value. The height of the catalyst layer had a variation of ± 2.7% with respect to the theoretical value. From this result, it was found that in the plate reactor having the partition, the catalyst can be filled very uniformly into the gap by filling the catalyst in each compartment.

(Example 6)
The calculation method of the conversion rate of the reaction raw material, the selectivity of the target reaction product, the yield of the target reaction product, and the loading amount of the reaction raw material used in the present example relating to the third production method of the reaction product Described below.
<1> Conversion rate of reaction raw materials (propylene, acrolein, etc.) [%] =
(Mole number of reaction raw material converted to other substance in reactor) / (Mole number of reaction raw material supplied to reactor) × 100
<2> Selectivity of target reaction product [%] = (number of moles of target reaction product at reactor outlet) / (number of moles of reaction raw material converted to other substances in reactor) x 100
<3> Yield of target reaction product [%] =
(Mole number of target reaction product at reactor outlet) / (Mole number of reaction raw material supplied to reactor) × 100
<4> Load of reaction raw material [NL / L · hr] =
Hourly supply amount of reaction raw material L [liter] [converted to standard state] / catalyst amount provided for reaction L [liter]
Here, the standard state refers to a state at a temperature of 0 ° C. and 101.325 kPa (absolute pressure).

In the production of acrylic acid by catalytic vapor phase oxidation of propylene with molecular oxygen, Mo (12) Bi (5) Co (3) Ni (2) Fe () is used as a pre-stage catalyst for converting propylene to acrolein and acrylic acid. A metal oxide powder having a composition of 0.4) Na (0.4) B (0.2) K (0.08) Si (24) O (x) was prepared and molded to obtain an outer diameter of 4 mmφ, A cylindrical pellet catalyst having a height of 3 mm was obtained. Furthermore, as a catalyst for the latter stage for converting acrolein to acrylic acid, the composition of Mo (12) V (2.4) Ni (15) Nb (1) Cu (1) Sb (59) Si (7) O (x) A metal oxide powder was prepared, and this powder was molded to obtain a ring-shaped catalyst having an outer diameter of 5 mmφ, an inner diameter of 2 mmφ, and a height of 3 mm. Here, (x) of O (x) is a value determined by the oxidation state of each metal oxide.

A plate reactor having the structure shown in FIG. 42 was used. Two thin corrugated stainless steel plates (thickness 1 mm) were joined to form a heat medium flow path for adjusting the reaction temperature. Table 4 shows the period (L), height (H), and wave number of the waveform shape shown in FIG.

A pair of the corrugated heat transfer plates joined to each other was filled with a pre-stage catalyst in a pre-reactor and a post-stage catalyst in a post-reactor to form a catalyst layer. As shown in Table 4, the catalyst layers of the upstream reactor and the downstream reactor are changed to the reaction zone (S1), reaction zone (S2), and reaction zone (S3) from the upstream in the flow direction of the reaction gas as shown in Table 4. Divided. A pair of corrugated heat transfer plates were installed in parallel as shown in FIG. 42, and the interval (P shown in FIG. 43) was adjusted to 26 mm. The width of the heat transfer plate was 114 mm.

The amount of catalyst shown in Table 4 is the result of volume measurement measured by pouring water from the top with a plate attached to the bottom of the catalyst layer with each reactor vertical. The amount of the catalyst was used for calculating the amount of reaction raw material.

As a reaction raw material, a reaction raw material mixture (hereinafter referred to as reaction mixed gas) containing 9.5 mol% of propylene was vented from the inlet (reaction zone (S1)) of the preceding reactor. In addition to propylene, the reaction gas mixture contains 15.2 mol% oxygen, 65.9 mol% nitrogen, and 9.4 mol% water vapor.

The above-mentioned pre-stage catalyst was filled in the pre-stage reactor shown in Table 4, and propylene oxidation reaction was performed. NeoSK-OIL (registered trademark) 1400 manufactured by Soken Technics Co., Ltd. was used as the heat medium, and the temperature was adjusted and then supplied to the reaction zone (S1) to (S3). The supply amount of the heat medium was such that the flow rate of the heat medium was 0.7 m or more per second.

A reaction mixed gas having a propylene concentration of 9.5 mol% was supplied to the inlet of the reactor at a rate of 5,670 liters per hour [standard state (temperature 0 ° C., 101.325 kPa) conversion]. The temperature of the heat medium supplied to each reaction zone (S1), (S2), and (S3) was 342 ° C., 329 ° C., and 329 ° C., respectively. The amount of propylene supplied was 539 liters per hour [converted to a standard state (temperature 0 ° C., 101.325 kPa)] (hereinafter also referred to as NL / Hr). The pressure at the inlet of the reactor was 0.109 MPaG (megapascal gauge), and the pressure difference (pressure loss) between the inlet and the outlet of the catalyst layer of the reactor was as small as 14 kPa.

When the outlet gas was analyzed by gas chromatography, the conversion of propylene was 97.2%, the yield of acrylic acid was 10.1%, and the yield of acrolein was 81.7%. The amount of propylene loaded was 167 liters per hour [converted to a standard state (temperature 0 ° C., 101.325 kPa)] (hereinafter also referred to as NL / L · Hr).

(Example 7)
The reaction was carried out in the same manner as in Example 6 except that the temperature of the heat medium supplied to each reaction zone (S1), (S2), and (S3) was adjusted to 360 ° C, 345 ° C, and 329 ° C, respectively. When the outlet gas was analyzed by gas chromatography, the conversion of propylene was 98.3%, and the total yield of acrylic acid and acrolein was 92.7%.

(Example 8)
The supply amount of the reaction gas mixture was increased to 7,817 liters per hour [standard state (temperature 0 ° C., 101.325 kPa) conversion] and supplied to each reaction zone (S1), (S2), and (S3). The reaction was carried out in the same manner as in Example 6 except that the temperature of the heat medium was adjusted to 342 ° C, 335 ° C, and 334 ° C, respectively. The supply rate of propylene was 743 NL / Hr.

When the outlet gas was analyzed by gas chromatography, the conversion of propylene was 95.4%, the yield of acrylic acid was 11.5%, and the yield of acrolein was 79.2%. The amount of propylene loaded was 231 NL / L · Hr. The pressure at the reactor inlet was 0.134 MPaG (megapascal gauge), and the pressure loss of the catalyst layer of the reactor was 30 kPa (kilopascal).

Example 9
The reactor outlet gas obtained in Example 8 was supplied to the subsequent reactor to oxidize acrolein to produce acrylic acid. As a source of molecular oxygen for the oxidation reaction, air is converted to 2,186 per hour [standard state (temperature 0 ° C., 101.325 kPa) conversion] and nitrogen is 680 liters per hour [standard state (temperature 0 ° C., 101.325 kPa). ) Conversion] was mixed with the upstream reactor outlet gas and fed to the downstream reactor.

The temperature of the heat medium supplied to each reaction zone (S1), (S2), and (S3) of the post-stage reactor was 284 ° C, 278 ° C, and 278 ° C, respectively. The supply amount of the heat medium was set such that the flow rate in the heat medium flow path in the reaction zone was 0.4 m / second or more. The pressure at the downstream reactor inlet was 0.097 MPaG ((megapascal gauge)), and the pressure loss in the catalyst layer of the reactor was 29 kPa (kilopascal).

When the outlet gas was analyzed by gas chromatography, the conversion of acrolein was 99.4%, and the yield of acrylic acid relative to propylene supplied to the preceding reactor was 86.3%. The load of acrolein was 201 NL / L · Hr.

(Examples 10 to 12 and Comparative Examples 3 and 4)
The reaction gas mixture used for the reaction is composed of 9.4 mol% propylene, 15.2 mol% oxygen, 65.9 mol% nitrogen, and 9.5 mol% water vapor, and the propylene load is 219 NL / L. The reaction was carried out in the same manner as in Example 6 except that it was supplied with Hr and the temperature of the heat medium supplied to each reaction zone (S1), (S2), and (S3) was adjusted to the temperature shown in Table 2. Carried out. Table 5 shows the analysis results of the outlet gas analyzed by gas chromatography. The reaction was continued for 230 hours or more, but the conversion rate and yield were stable and there was no sign of catalyst deterioration.

(Example 13 and Comparative Example 5)
A plate type reactor having the same period (L), height (H), wave number, and corrugated plate interval P shown in Table 4 but having a heat transfer plate width of 96 mm is used. It was. The heat transfer plate reactor was filled with the latter catalyst. The filling height was 1.8 m, and the catalyst amount was 2.5 L (liter).

As a comparative example 5, a stainless steel tube having an inner diameter of 27 mm was used as a reaction tube, and a tubular reactor in which the reaction vessel was filled with a catalyst for a subsequent stage to a filling height of 1.8 m was prepared. The amount of catalyst was 1.0 L.

The above plate reactor and tube reactor were fixed vertically, air at room temperature was supplied from above, the inlet pressure and the outlet pressure were measured, and the pressure loss of the catalyst layer was determined. The results are shown in Table 6.

Here, the air flow [NL / L · Hr] represents the gas supply amount per hour of the catalyst 1 L (liter). In addition, the volume of the gas is used in the standard state (0 ° C., 101.325 kPa).
Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application includes Japanese patent applications filed on March 31, 2008 (Japanese Patent Application No. 2008-091298), Japanese patent applications filed on March 31, 2008 (Japanese Patent Application No. 2008-091705), and applications filed on March 31, 2008. This is based on a Japanese patent application (Japanese Patent Application No. 2008-091818) and a Japanese patent application filed on December 24, 2008 (Japanese Patent Application No. 2008-327973), the contents of which are incorporated herein by reference.

In the production of the plate reactor, the desired reaction result assumed at the time of design may not be obtained in the actual plate reactor because the arrangement of the heat transfer plate deviates from the design value. However, the first plate reactor and the manufacturing method thereof provide a technique for identifying an allowable error in the arrangement of the heat transfer plate and fixing the heat transfer plate within the range of the error. As a result, the technology for achieving the desired reaction results in an actual plate reactor by the first production method of the reaction product that controls the temperature of the heating medium without changing the structure of the plate reactor. It is expected that the possibility of establishing and using a plate reactor for industrial production of reaction products by gas phase catalytic reaction will be greatly expanded. Thus, further development in the field of production of reaction products by gas phase catalytic reaction is expected by the present invention.

In a plate reactor, the reaction may be controlled by adjusting the thickness of the catalyst layer. In such a plate reactor, it is much more difficult to charge the catalyst uniformly throughout the reactor, but the second plate reactor makes the proper filling of the catalyst quick, accurate and easy. It is expected that the workability in the installation, maintenance and regular inspection of the plate reactor will be greatly improved.

Further, according to the second production method of the reaction product, in the production method in which the reaction raw material is supplied to the plate reactor filled with the catalyst and the reaction raw material is reacted to produce the reaction product, It is expected that the reaction results are prevented from lowering due to variations, achieving the desired reaction results according to the performance of the catalyst, and further improving the reaction results with the improved catalyst.

Further, according to the third production method of the reaction product, in the production method of supplying a reaction raw material to a plate reactor filled with a catalyst and reacting the reaction raw material to produce a reaction product, the reaction per unit catalyst When the raw material processing load is increased, the pressure loss of the reaction gas passing through the catalyst is prevented from increasing, and the heat generated by the reaction is controlled appropriately to prevent hot spots and prevent damage to the catalyst. It is possible to improve the yield of the target reaction product.
Therefore, the industrial value of the present invention is remarkable.

Claims

A reaction vessel for reacting a gaseous raw material, a plurality of heat transfer plates provided side by side in the reaction vessel, a heat medium supply device for supplying a heat medium of a desired temperature to the heat transfer plate, Have
The heat transfer plate includes a plurality of heat transfer tubes connected at a peripheral edge or an edge of a cross-sectional shape,
In the plate reactor which is a device for supplying a heat medium to a heat transfer tube of a heat transfer plate housed in a reaction vessel, the heat medium supply device,
In the gap between the heat transfer plates facing each other, the design value of the distance between the surfaces of the heat transfer plates in the direction orthogonal to the surface equidistant from the surface formed by the axis of the heat transfer plate is 5 to 50 mm, A plate reactor characterized in that the difference between the measured values of the distance between the surfaces with respect to the design value is -0.6 to +2.0 mm.
The plate reactor according to claim 1, wherein the heat transfer plate has an axial length of 5 m or less.
The plate reactor according to claim 1 or 2, further comprising a spacer for forming a predetermined interval between the heat transfer plates.
The heat transfer plate is formed by joining two steel plates formed so that a plurality of shapes obtained by dividing the cross-sectional shape of the heat transfer tube into two by the shaft of the heat transfer plate are connected. The plate reactor according to any one of the above.
The plate type according to any one of claims 1 to 4, wherein a difference in an actual measurement value of the distance between the surfaces with respect to the design value is smaller on the upstream side in the direction of flow of the raw material gas in the gap. Reactor.
The difference between the measured values of the distance between the surfaces with respect to the design value at a position where the reaction rate of the raw material in the raw material gas is 70% or less is between the surfaces with respect to the design value at a position where the reaction rate is greater than 70%. The plate reactor according to claim 5, wherein the plate reactor is smaller than a difference in measured values of the distance.
The plate reactor according to any one of claims 1 to 6, wherein the total volume of the gap is 3L or more.
The plate type according to any one of claims 1 to 7, further comprising a temperature measuring device for measuring temperatures at two or more positions of the catalyst layer in which the catalyst is filled in the gap. Reactor.
A reaction vessel is provided with a plurality of heat transfer plates arranged side by side, and a catalyst is formed by filling a gap between the heat transfer plates with a catalyst to form a catalyst layer. And a step of supplying a heat medium at a predetermined temperature to a plurality of heat transfer tubes constituting the heat transfer plate, by reacting the raw material gas in the presence of the catalyst, In the method for producing a reaction product for producing a reaction product,
The plate reactor according to any one of claims 1 to 8, which is used as the plate reactor,
A method for producing a reaction product, characterized in that a heat medium having a temperature at which the peak temperature of the catalyst layer is set to a set value of the peak temperature of the catalyst layer set at the time of designing the plate reactor is supplied to the heat transfer tube. .
The method for producing a reaction product according to claim 9, wherein the reaction of the raw material in the raw material gas in the presence of a catalyst is an exothermic reaction.
The reaction product is one or both of acrolein and acrylic acid, one or both of methacrolein and methacrylic acid, maleic acid, phthalic acid, ethylene oxide, paraffin, alcohol, acetone and phenol, or butadiene, The method for producing a reaction product according to claim 10.
A reaction vessel for reacting gaseous raw materials, a plurality of heat transfer plates provided in line with the reaction vessel, and a heat medium supply device for supplying a heat medium of a desired temperature to the heat transfer plate. And
The heat transfer plate includes a plurality of heat transfer tubes connected at a peripheral edge or an edge of a cross-sectional shape,
In the method of manufacturing a plate reactor, the heating medium supply device is a device for supplying a heating medium to a heat transfer tube of a heat transfer plate housed in a reaction vessel.
The heat transfer plates are arranged at intervals such that the distance between the surfaces of the heat transfer plates in the direction perpendicular to the surface that is equidistant from the surface of the heat transfer plate in the gap between the opposing heat transfer plates is the design value. And a method of manufacturing a plate reactor, comprising the step of joining the heat transfer tube and the heat medium supply device.
For the heat transfer plate, a heat transfer plate formed by joining two steel plates formed so that a plurality of shapes obtained by dividing the cross-sectional shape of the heat transfer tube into two by the shaft of the heat transfer plate is used,
13. The method for manufacturing a plate reactor according to claim 12, wherein the formed steel plate is a formed steel plate having an error with respect to a design value of forming the steel plate within ± 0.5 mm.
The method for manufacturing a plate reactor according to claim 12, wherein a heat transfer plate having an axial length of 5 m or less is used as the heat transfer plate.
A step of arranging the heat transfer plate in the reaction vessel before joining with the heat medium supply device via a spacer that forms an interval between the heat transfer plates so that the distance between the surfaces of the heat transfer plates is a design value; The method for manufacturing a plate reactor according to any one of claims 12 to 14, wherein the plate reactor is included.
A reaction vessel for reacting reaction raw materials, a heat transfer tube, a plurality of heat transfer plates provided in line in the reaction vessel, and a device for supplying a heat medium to the heat transfer tube,
The reaction vessel is a vessel in which the supplied reaction raw material is discharged through a gap between adjacent heat transfer plates,
The heat transfer plate includes a plurality of the heat transfer tubes connected at a peripheral edge or an edge of a cross-sectional shape,
In a plate reactor in which a catalyst is filled in a gap between adjacent heat transfer plates,
A plate reactor, further comprising a partition that partitions a gap between adjacent heat transfer plates into a plurality of compartments containing a packed catalyst along a ventilation direction in the reaction vessel.
The plate reactor according to claim 16, wherein the plurality of compartments have the same volume.
The plate reactor according to claim 16 or 17, wherein each of the plurality of compartments has a volume of 1 to 100L.
The plate reactor according to any one of claims 16 to 18, wherein each of the plurality of compartments has a volume of 2 to 25L.
A plurality of vent plugs which have air permeability, are detachably fixed to the end portions of the respective compartments, and close the end portions of the respective compartments so as to hold the catalyst accommodated in the respective compartments. Item 20. The plate reactor according to any one of Items 16 to 19.
One or both of the partition and the heat transfer plate have a first locking portion for locking the vent plug,
The vent plug has a vent plate that is breathable and impervious to the catalyst, a skirt portion that is provided perpendicularly to the vent plate at a part or all of the periphery of the vent plate, and provided in the skirt portion. 21. The plate reactor according to claim 20, further comprising a first locking portion and a second locking portion that is detachably locked.
The plate reactor according to any one of claims 16 to 21, wherein an interval between the plurality of partitions is 0.1 to 1 m.
A method for producing a reaction product using the plate reactor according to any one of claims 16 to 22,
Supplying a heat medium having a desired temperature to the heat transfer tube, supplying a reaction raw material to a gap between adjacent heat transfer plates filled with a catalyst, and obtaining a reaction product discharged from the gap; Including
The reaction 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 1 selected from the group consisting of unsaturated aliphatic aldehydes having 3 and 4 carbon atoms. Species; hydrocarbons having 4 or more carbon atoms; xylene and / or naphthalene; olefins; carbonyl compounds; cumene hydroperoxide; butenes;
The 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; Or styrene.
(A) a plate reactor having a catalyst layer formed between heat transfer plates, at least one reaction raw material selected from the group consisting of hydrocarbons having 3 and 4 carbon atoms and tertiary butanol; and Supplying a reaction raw material mixture containing molecular oxygen, catalytic vapor phase oxidation of the reaction raw material, and at least one selected from the group consisting of unsaturated hydrocarbons and unsaturated aliphatic aldehydes having 3 and 4 carbon atoms Producing a reaction product, or
(B) A plate-type reactor provided with a catalyst layer formed between heat transfer plates, which is a production method, comprising at least a reaction raw material selected from the group consisting of unsaturated aliphatic aldehydes having 3 and 4 carbon atoms A reaction raw material mixture containing one kind and molecular oxygen is supplied, and the reaction raw material is subjected to catalytic gas phase oxidation to produce at least one reaction product selected from the group consisting of unsaturated fatty acids having 3 and 4 carbon atoms. In the way to
The plate reactor is divided into a plurality of reaction zones having different average layer thicknesses of the catalyst layers, and a heat medium whose temperature is independently adjusted is supplied to the plurality of reaction zones. The heat generated is removed through the heat transfer plate, and the temperature in the catalyst layer is independently controlled,
The temperature T (S1) of the heating medium supplied to the reaction zone S1 closest to the inlet of the reaction raw material mixture is adjacent to the reaction zone S1 and is located downstream of the flow of the reaction raw material mixture. Higher than the temperature T (S2) of the heat medium supplied to
The load of the reaction raw material when oxidizing at least one of the reaction raw materials selected from the group consisting of the hydrocarbons having 3 and 4 carbon atoms and tertiary butanol is 150 liters per hour per liter of catalyst [standard state (Temperature 0 ° C., 101.325 kPa) conversion]
When oxidizing at least one kind of the reaction raw material selected from the group consisting of the unsaturated aliphatic aldehydes having 3 and 4 carbon atoms, the loading amount of the reaction raw material is 160 liters per hour per 1 liter of catalyst [standard state (temperature Selected from the group consisting of unsaturated hydrocarbons, unsaturated aliphatic aldehydes having 3 and 4 carbon atoms, and unsaturated fatty acids having 3 and 4 carbon atoms, characterized in that A production method for producing one or more reaction products.
The temperature of the heat medium supplied to any unspecified reaction zone S (j) is T (Sj), and the reaction zone S (adjacent to the reaction zone S (j) and positioned downstream of the flow of the reaction raw material mixture ( When the temperature of the heat medium supplied to j + 1) is T (Sj + 1), T (Sj) and T (Sj + 1) satisfy the relationship T (Sj) −T (Sj + 1) ≧ 5 25. The manufacturing method according to claim 24, wherein:
The number of the reaction zones is 2 to 5, and the average layer thickness of the catalyst layer in each reaction zone increases from the inlet to the outlet of the reaction raw material mixture. Manufacturing method.
When oxidizing at least one of the reaction raw materials selected from the group consisting of the hydrocarbons having 3 and 4 carbon atoms and tertiary butanol, the loading amount of the reaction raw materials is 170 to 290 liters per liter of catalyst per hour [ The production method according to any one of claims 24 to 26, which is in a standard state (converted at a temperature of 0 ° C and 101.325 kPa).
When oxidizing at least one reaction raw material selected from the group consisting of the unsaturated aliphatic aldehydes having 3 and 4 carbon atoms, the loading amount of the reaction raw material is 180 to 300 liters per liter of catalyst [standard state] The production method according to any one of claims 24 to 27, wherein the temperature is (converted at a temperature of 0 ° C and 101.325 kPa).
The production method according to any one of claims 24 to 28, wherein the conversion rate of the reaction raw material at the reaction product outlet of the plate reactor is 90% or more.
The production method according to any one of claims 24 to 29, wherein the reaction raw material is propylene, and the temperature of the heat medium supplied to the plurality of reaction zones is 320 to 400 ° C.
The production method according to any one of claims 24 to 29, wherein the reaction raw material is acrolein, and the temperature of the heat medium supplied to the plurality of reaction zones is 250 to 320 ° C.