CN101977678A - Plate type reactor, manufacturing method therefor, and reaction product manufacturing method using the plate type reactor - Google Patents

Plate type reactor, manufacturing method therefor, and reaction product manufacturing method using the plate type reactor Download PDF

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Publication number
CN101977678A
CN101977678A CN2009801103159A CN200980110315A CN101977678A CN 101977678 A CN101977678 A CN 101977678A CN 2009801103159 A CN2009801103159 A CN 2009801103159A CN 200980110315 A CN200980110315 A CN 200980110315A CN 101977678 A CN101977678 A CN 101977678A
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plate
heat transfer
type reactor
mentioned
catalyst
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矶谷真治
神野公克
坂仓康之
川谷洋治
矢田修平
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Mitsubishi Kasei Corp
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Mitsubishi Kasei Corp
Mitsubishi Chemical Engineering Corp
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Priority claimed from JP2008327973A external-priority patent/JP6088120B2/en
Application filed by Mitsubishi Kasei Corp, Mitsubishi Chemical Engineering Corp filed Critical Mitsubishi Kasei Corp
Priority to CN201510118079.2A priority Critical patent/CN104803834A/en
Publication of CN101977678A publication Critical patent/CN101977678A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/248—Reactors comprising multiple separated flow channels
    • B01J19/249—Plate-type reactors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2451—Geometry of the reactor
    • B01J2219/2453—Plates arranged in parallel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2451—Geometry of the reactor
    • B01J2219/2456—Geometry of the plates
    • B01J2219/2459—Corrugated plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2461—Heat exchange aspects
    • B01J2219/2462—Heat exchange aspects the reactants being in indirect heat exchange with a non reacting heat exchange medium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2469—Feeding means
    • B01J2219/2471—Feeding means for the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2476—Construction materials
    • B01J2219/2477—Construction materials of the catalysts
    • B01J2219/2481—Catalysts in granular from between plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2491—Other constructional details
    • B01J2219/2497—Size aspects, i.e. concrete sizes are being mentioned in the classified document
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2491—Other constructional details
    • B01J2219/2498—Additional structures inserted in the channels, e.g. plates, catalyst holding meshes

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 ho ogeneously 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-type reactor, its preparation method and use plate-type reactor are made the manufacture method of reaction product
Technical field
The present invention relates to plate-type reactor, its preparation method and use the manufacture method of above-mentioned plate-type reactor by gas phase haptoreaction manufacturing reaction product, described plate-type reactor is used to be accompanied by the heat release of use catalyst or the reaction of heat absorption.
In addition, the present invention relates to plate-type reactor and in the plate-type reactor that is filled with catalyst supply response raw material and this reaction raw materials is reacted make the manufacture method of reaction product.
Background technology
As the raw material that in the presence of solid catalyst, the makes gaseous state employed reactor in the gas phase haptoreaction of the reaction product that obtains gaseous state that reacts, the multi-tubular reactor of catalyst filling (for example in the known reaction tube that for example has in reaction vessel, with reference to patent documentation 1) and 2 above heat transfer plates in reaction vessel between the plate-type reactor (for example, with reference to patent documentation 2 and 3) of gap catalyst filling.
These used reactors require to make with high accuracy usually in the gas phase haptoreaction.For example, if the caliber error of the heat-transfer pipe of reaction tube in multi-tubular reactor or the formation heat transfer plate in the plate-type reactor is big, the part of heat extraction variation can appear partly then, at part catalyst layer runaway reaction, and may the local deterioration that catalyst takes place.But,, then in the making of reactor, may need very a large amount of artificial, a large amount of steel if will make reactor with high accuracy more.
In multi-tubular reactor,, can improve the precision of reactor with comparalive ease by the high steel pipe of service precision in reaction tube.On the other hand, the heat-transfer pipe in the plate-type reactor is made usually in the following way: a plurality of continuous modes of shape that are divided into two with the cross sectional shape with heat-transfer pipe are steel formability, and the flange in the steel plate after will being shaped is welded to one another, and make thus.In addition, in plate-type reactor, the cross sectional shape of heat-transfer pipe or sectional dimension are usually from considering to determine to the thickness of the catalyst layer that is formed at the gap between heat transfer plate or the aspect that form is adjusted.Thereby, in the making of plate-type reactor, the various factors that makes when during steel plate generation warpage when can not get desired shape in the shaping of above-mentioned steel plate, after shaping and owing to the welding of steel plate warpage taking place etc. the precision of plate-type reactor take place to reduce can cause being difficult to produce high-precision plate-type reactor, the therefore control that can not react fully sometimes.
Therefore, the form of the heat transfer plate in the plate-type reactor and the main difficulty in the manufacture method are the high accuracy making of plate-type reactor.Heat-exchangers of the plate type has and the plate-type reactor similar structures having on the heat transfer plate this point that is made of heat-transfer pipe, it has been generally acknowledged that for heat-exchangers of the plate type the worst error with respect to the setting value of the distance between heat transfer plate is about 3～5mm or more than it.
But in the gas phase haptoreaction of heat release that is attended by the use catalyst or heat absorption, it is very important that reaction temperature is carried out strict control.If the control of the temperature of catalyst layer is insufficient, the deterioration of catalyst or the yield of goal response product then can take place reduce.Therefore, if the precision of plate-type reactor is low, for example, if the error with respect to the setting value of the distance between heat transfer plate is big, the part of heat extraction variation then can partly occur, it is out of control to react at the part catalyst layer, and the deterioration of catalyst, the yield reduction of reaction product can take place in the part.On the other hand, if pay attention to the raising of plate-type reactor precision, then need very a large amount of artificial, a large amount of steel in the making of plate-type reactor, productivity ratio can reduce in the manufacturing of the reaction product that uses such reactor, can not be practical in the industry of reaction product is made.
As the gas phase contact oxidation of propane, propylene or methacrylaldehyde such, be attended by heat release or heat absorption and use the used reactor of gas-phase reaction of granular solid catalyst, for example known have a following plate-type reactor: this plate-type reactor has the reaction vessel that is used to the vapor reaction raw material is reacted, has heat-transfer pipe and be arranged side by side 2 above heat transfer plates in above-mentioned reaction vessel and the device of above-mentioned heat-transfer pipe being supplied with the thermal medium body; Above-mentioned reaction vessel is for supplying with the container that next gas is discharged from by the gap between adjacent heat transfer, above-mentioned heat transfer plate comprises the above-mentioned heat-transfer pipe more than 2 that is connected with the periphery of cross sectional shape or ora terminalis, gap between adjacent heat transfer is filled with catalyst (for example, referring to patent documentation 3).
Such plate-type reactor has the catalyst layer more than 2 in the gap between the adjacent heat transfer of being formed at usually, and the contact excellence of heat transfer plate and catalyst, thereby can efficient make a large amount of products well by above-mentioned gas-phase reaction, consider that from this respect it is excellent.
On the other hand, in above-mentioned gas-phase reaction, consider, wish the occupied state homogenising of catalyst from the aspect of control gas-phase reaction.In plate-type reactor, fill catalyst in gap between adjacent heat transfer with stratiform, thereby in above-mentioned each gap and all be difficult to regularly (certain To) catalyst filling in the gap, wish to develop can be in above-mentioned gap the even technology of catalyst filling.
In addition, be not filled under the situation in above-mentioned gap regularly at catalyst or under the situation of the part catalyst generation deterioration in above-mentioned gap, whole catalyst in its gap need be taken out and carry out the fillings of catalyst once more.Therefore, wish to develop the technology that easily to adjust the occupied state of the catalyst in the above-mentioned gap.
At present,, consider, use the multi-tubular reactor of tubing heat exchanger shape from the viewpoint of industrialness and practicality utilizing catalytic gas phase oxidation reaction to make in the manufacture method of product such as unrighted acid.In the manufacture method of the product of using this multi-tubular reactor, solid catalyst is filled in inboard at the reaction tube of multi-tubular reactor, make through temperature controlled thermal medium body in the outside of reaction tube and to circulate, utilize this thermal medium body that the temperature of reaction tube inboard is controlled.
State multi-tubular reactor in the use and make under the situation of product such as unrighted acid, when wanting to increase the manufacture of product, need to increase the number of reaction tube sometimes according to the increase of manufacture.But in this case, it also is possible that reaction tube reaches tens thousand of, exceeds the making limit of multi-tubular reactor sometimes.Surpass under the situation of making limit, the fact is the reaction series of having to have more than 2.
On the other hand, in the reaction tube number or reactor of regulation, need to improve the processing load of unit catalyst sometimes to guarantee desired manufacture.The reaction heat that produced in each reaction tube this moment increases, and can produce can not be by the situation of the temperature of reaction tube inboard suitably being controlled at the thermal medium body of reaction tube outside circulation.Under situation about can not suitably control to the temperature of reaction tube inboard, the temperature that remains on the part catalyst of reaction tube inboard significantly rise (hereinafter being also referred to as heat spot (hot spot)).Under the situation that the temperature of this part catalyst goes beyond the limit, the part catalyst damages, and the durability period of catalyst shortens.
The part catalyst takes place need stop using the production of the product of this reactor under the situation of damage, carries out the catalyst exchange.That is, the production of product stops during exchange catalysts, produces to be difficult to guarantee desired significant problems such as manufacture.In addition, even seriously do not arrive the degree of catalyst exchange,, can produce the reaction achievement variation of catalyst, the problems such as productive rate reduction of goal response product because the generation of heat spot also is difficult to keep appropriate reaction conditions.
In addition, in patent documentation 4 and 5, the method for using above-mentioned multi-tubular reactor that propylene or methacrylaldehyde as reaction raw materials are carried out catalytic gas phase oxidation reaction has been proposed under the state of the processing load that improves the unit catalyst.But there is following shortcoming: because used reaction tube is that radius is 20～30 millimeters a pipe in the multi-tubular reactor, and use inlet from reacting fluid (general names of the mixture of reacting material mixture, reaction product etc.) to exporting the identical reaction tube of caliber, thereby under the high condition of the processing load of the unit catalyst of reacting fluid, the pressure loss of reacting fluid is big, pressure in the reactor rises, and the result is that the productive rate of goal response product reduces.Further, be accompanied by the rising of pressing in the reactor, the energy that is used for the compressor of supply response fluid etc. increases, and is except unfavorable to the productive rate of goal response product, also unfavorable aspect cost.
A method as addressing the above problem has motion to propose to have the reactor for contact vapor-phase oxidation of heat-exchangers of the plate type structure.For example, in patent documentation 2, proposed between 2 heat transfer plates catalyst filling, supply with the board-like catalyst reaction equipment of thermal medium body to the outside of heat transfer plate.In addition, following board-like hydrogen-catalyst reactor has been proposed in patent documentation 3: make by figuration be circular arc or elliptic arc 2 ripple plates relatively to, the ripple plate convex surface part that will be bonded with each other a plurality of assortments of heat transfer plate that are formed with 2 above thermal medium body streams by the convex surface part that makes this two ripples plate and make adjacent heat transfer relative with concave surface portion to, thereby form the catalyst layer of predetermined space.
In above-mentioned motion, although the structure of having recorded and narrated plate-type reactor with and application in catalytic gas phase oxidation reaction, the heat that generates for control reaction suitably but there is no any mentioning with the method that the prevention heat spot improves the productive rate of goal response product simultaneously.Particularly, there is no any mentioning for the heat of when improving the processing load of unit catalyst, suitably controlling the reaction generation with the generation of prevention heat spot, the damage that prevents catalyst and the productive rate of raising goal response product and the method for manufacture.
Patent documentation 1: TOHKEMY 2004-000944 communique
Patent documentation 2: TOHKEMY 2004-167448 communique
Patent documentation 3: TOHKEMY 2004-202430 communique
Patent documentation 4: Japanese Unexamined Patent Application Publication 2003-514788 communique
Patent documentation 5: Japanese Unexamined Patent Application Publication 2002-539103 communique
Summary of the invention
The invention provides in the manufacturing of reaction product, can prevent to react out of control and can be used in the plate-type reactor of the manufacturing of large-duty reaction product.
In addition, the invention provides in the method for using plate-type reactor to carry out to prevent in the manufacturing of reaction product react out of control and making reaction product with high production rate.
In addition, the invention provides can be evenly and the plate-type reactor of the gap catalyst filling between adjacent heat transfer easily.
And the invention provides can be evenly and the gap catalyst filling between adjacent heat transfer and can easily adjust the plate-type reactor of the occupied state of the catalyst in the above-mentioned gap easily.
Further, the invention provides a kind of method of novelty, it is a supply response raw material and this reaction raw materials is reacted make the manufacture method of reaction product in the plate-type reactor that is filled with catalyst, in described manufacture method, even raising is when the processing load of the reaction raw materials of unit catalyst, also can prevent increase by the reaction gas pressure loss of catalyst, and can prevent the generation of heat spot by suitably controlling the heat that produces by reaction, and when preventing the catalyst damage, improve the yield of goal response product.
The invention provides following technology: promptly, by will with respect to the surface spacing of heat transfer plate from the range of allowable error of design load be set in-0.6～+ 2.0mm, thereby the temperature control to plate-type reactor does not cause obstacle, do not rely on the dilution of the use of low activity catalyst and catalyst and the manufacturing cost of plate-type reactor is maintained low cost, utilize industrial advantageous method to make valuable product simultaneously.
Promptly, the invention provides following plate-type reactor: this plate-type reactor has the reaction vessel that is used for gaseous feed is reacted, is arranged side by side at 2 above heat transfer plates of above-mentioned reaction vessel and the thermal medium feedway that is used for supplying with to above-mentioned heat transfer plate the thermal medium of desired temperature, above-mentioned heat transfer plate comprises 2 above heat-transfer pipes that link with the periphery of cross sectional shape or ora terminalis, and above-mentioned thermal medium feedway is supplied with the device of thermal medium for the heat-transfer pipe of the heat transfer plate in being contained in reaction vessel; In described plate-type reactor, the design load of the distance between the surface of above-mentioned heat transfer plate is 5～50mm, the difference of the measured value of the distance between above-mentioned surface and above-mentioned design load is-0.6～+ 2.0mm (hereinafter being also referred to as " first plate-type reactor "), distance between the surface of above-mentioned heat transfer plate be relatively to above-mentioned heat transfer plate between the gap in, with the direction of equidistant the quadrature of face that constitutes apart from axle by above-mentioned heat transfer plate on distance.
In addition, the invention provides first plate-type reactor, wherein, the axial length of above-mentioned heat transfer plate is preferably below the 5m, more preferably below the 2m.
In addition, the invention provides first plate-type reactor, this first plate-type reactor preferably further has the sept that is used for forming appointed interval between above-mentioned heat transfer plate.
In addition, the invention provides first plate-type reactor, wherein preferred above-mentioned heat transfer plate engages with two steel plates and forms, and these two steel plates are shaped as, and a plurality of axles with heat transfer plate link to each other the cross sectional shapes of the above-mentioned heat-transfer pipe shape that forms that is divided into two.
In addition, the invention provides first plate-type reactor, the upstream side of the ventilation direction of the unstrpped gas in the gap of difference between heat transfer plate of the measured value of the distance between wherein preferred above-mentioned surface and above-mentioned design load is littler.
In addition, the invention provides first plate-type reactor, wherein preferred is that the difference of the measured value of the distance position, between above-mentioned surface below 70% and above-mentioned design load is less than above-mentioned reactivity poor greater than the measured value of distance 70% position, between above-mentioned surface and above-mentioned design load in the raw material reaction rate in above-mentioned raw materials gas.
In addition, the invention provides first plate-type reactor, wherein the total measurement (volume) in preferred above-mentioned gap is more than the 3L.
In addition, the invention provides first plate-type reactor, wherein preferred above-mentioned first plate-type reactor further has temperature measuring apparatus, and this temperature measuring apparatus is used to measure the temperature of the position more than 2 places of the catalyst layer that catalyst is filled in above-mentioned gap and forms.
In addition, the invention provides the manufacture method of reaction product, this manufacture method is used and is provided with side by side in reaction vessel that 2 above heat transfer plates, the gap between heat transfer plate are filled with catalyst and the plate-type reactor that forms catalyst layer, above-mentioned manufacture method comprises and gaseous feed is supplied to above-mentioned reaction vessel and the operation by above-mentioned catalyst layer and to the operation of the thermal medium of 2 that constitute above-mentioned heat transfer plate above heat-transfer pipes supply predetermined temperatures, and this manufacture method reacts unstrpped gas in the presence of above-mentioned catalyst and generates the reaction product of gaseous state; In this manufacture method, plate-type reactor of the present invention is as above-mentioned plate-type reactor; Thermal medium is supplied to heat-transfer pipe (hereinafter being also referred to as " first manufacture method of reaction product "), and the temperature of thermal medium is that to make the peak temperature of above-mentioned catalyst layer be the temperature of setting value of the peak temperature of the catalyst layer that sets when design of plate-type reactor.
In addition, the invention provides first manufacture method of reaction product, wherein preferred in the presence of catalyst the reaction of the raw material in the unstrpped gas be exothermic reaction.
In addition, the invention provides first manufacture method of reaction product, wherein preferred above-mentioned reaction product is methacrylaldehyde and/or acrylic acid, MAL and/or methacrylic acid, maleic acid, phthalic acid, ethylene oxide, alkane, alcohol, acetone and phenol or butadiene.
Further, the invention provides the preparation method of plate-type reactor, described manufacture method is used to make following plate-type reactor: this plate-type reactor has and is used to reaction vessel that gaseous feed is reacted, be arranged side by side 2 above heat transfer plates in above-mentioned reaction vessel, and the thermal medium feedway that is used for supplying with the thermal medium of desired temperature to above-mentioned heat transfer plate, above-mentioned heat transfer plate comprises 2 above heat-transfer pipes that link with the periphery of cross sectional shape or ora terminalis, and above-mentioned thermal medium feedway is supplied with the device of thermal medium for the heat-transfer pipe of the heat transfer plate in being contained in reaction vessel; Wherein, this preparation method comprises following operation: relatively to heat transfer plate between the gap, become the arranged spaced heat transfer plate of design load with the distance between the surface of heat transfer plate, heat-transfer pipe is engaged with the thermal medium feedway, the distance between the surface of described heat transfer plate be with apart from by the distance on the direction of equidistant the quadrature of face that constitute of axle of described heat transfer plate.
In addition, the invention provides the preparation method of above-mentioned plate-type reactor, wherein preferred above-mentioned heat transfer plate uses by two steel plates and engages the heat transfer plate that forms, these two steel plates are shaped as, a plurality of axles with heat transfer plate link to each other the cross sectional shapes of the above-mentioned heat-transfer pipe shape that forms that is divided into two, the above-mentioned steel plate after the shaping use error with respect to the design load of the shaping of steel plate be ± 0.5mm is with interior shaping steel plate.
Perhaps the invention provides the preparation method of above-mentioned plate-type reactor, the axial length that wherein preferred above-mentioned heat transfer plate uses above-mentioned heat transfer plate as below the 5m, be preferably the heat transfer plate below the 2m.
In addition, the invention provides the preparation method of above-mentioned plate-type reactor, wherein preferred this preparation method further comprises following operation: across being used for forming sept at interval between heat transfer plate, with the engaging of thermal medium feedway before in reaction vessel, dispose heat transfer plate, described interval is the interval that the distance between the surface of above-mentioned heat transfer plate becomes design load.
And the present invention also provides plate-type reactor, wherein preferred in plate-type reactor the gap between adjacent heat transfer form can hold catalyst 2 with upper curtate along the circulating direction of reaction raw materials, at each section catalyst filling regularly.
In addition, the invention provides plate-type reactor, wherein preferred in plate-type reactor the gap between adjacent heat transfer form can hold catalyst 2 with upper curtate along the circulating direction of reaction raw materials, further can carry out the filling and the taking-up of catalyst independently at each section.
Promptly, the invention provides a kind of plate-type reactor, this plate-type reactor has the reaction vessel that is used to reaction raw materials is reacted, the device that has heat-transfer pipe and be arranged side by side 2 above heat transfer plates in above-mentioned reaction vessel and be used for supplying with to above-mentioned heat-transfer pipe the thermal medium body; The container that above-mentioned reaction vessel is discharged from by the gap between adjacent heat transfer for the reaction raw materials of being supplied with; Above-mentioned heat transfer plate comprises the above-mentioned heat-transfer pipe more than 2 that links with the periphery of cross sectional shape or ora terminalis; Gap between adjacent heat transfer is filled with catalyst; In described plate-type reactor, this plate-type reactor further has the gap between adjacent heat transfer is divided into 2 dividing plates with upper curtate (bodyguard is cut り) (hereinafter being also referred to as " second plate-type reactor ") that hold the catalyst of being filled along the ventilation direction in the reaction vessel.
In addition, the invention provides second plate-type reactor, wherein preferred above-mentioned 2 identical with upper curtate volume separately.
In addition, the invention provides second plate-type reactor, wherein preferred above-mentioned 2 is 1～100L with upper curtate volume separately.
In addition, the invention provides second plate-type reactor, wherein preferred above-mentioned 2 is 2～25L with upper curtate volume separately.
In addition, the invention provides second plate-type reactor, wherein preferred described plate-type reactor further has 2 above breather plugs, and described breather plug has aeration, can be fixed on the end of each section, the end of inaccessible each section is to keep being contained in the catalyst in each section with freely loading and unloading.
In addition, the invention provides second plate-type reactor, wherein preferred aforementioned barriers and/or heat transfer plate have and are used to first fastener that card ends above-mentioned breather plug; Above-mentioned breather plug has vent board, skirt section and second fastener, and above-mentioned vent board has aeration, does not see through catalyst simultaneously; Above-mentioned skirt section vertically is provided with respect to vent board in part or all of the periphery of vent board; Above-mentioned second fastener is located at above-mentioned skirt section, can freely block with above-mentioned first fastener with loading and unloading and end.
In addition, the invention provides second plate-type reactor, wherein preferred above-mentioned 2 0.1～1m that are spaced apart with upper spacer.
In addition, the invention provides a kind of method, it is preferably the method for using second plate-type reactor to make reaction product,
Wherein, this method comprise to above-mentioned heat-transfer pipe supply with the operation of the thermal medium body of desired temperature, between the adjacent heat transfer that is filled with catalyst gap supply response raw material and discharge to obtain the operation of reaction product from above-mentioned gap;
Above-mentioned reaction raw materials is an ethene; Being selected from by carbon number is at least a in the group formed of 3 and 4 the hydrocarbon and the tert-butyl alcohol or to be selected from by carbon number be at least a in the group formed of 3 and 4 unsaturated aliphatic aldehyde; Carbon number is the hydrocarbon more than 4; Dimethylbenzene and/or naphthalene; Alkene; Carbonyls; Cumene hydroperoxide; Butylene; Or ethylbenzene;
Above-mentioned reaction product is an ethylene oxide; Carbon number is that 3 and 4 unsaturated aliphatic aldehyde and/or carbon number are 3 and 4 unrighted acid; Maleic acid; Phthalic acid; Alkane; Alcohol; Acetone and phenol; Butadiene; Or styrene (hereinafter being also referred to as " second manufacture method of reaction product ").
Further, the inventor furthers investigate in order to solve above-mentioned problem, supply response raw material and this reaction raw materials catalytic gas phase oxidation is come in the manufacture method of manufacturing objective reaction product in the plate-type reactor that is split into 2 different above conversion zones of the average layer thickness that is formed at the catalyst layer between the heat transfer plate, be conceived to be supplied to the temperature of the thermal medium body in above-mentioned 2 above conversion zones, thereby finished the present invention.That is, main points of the present invention are as follows.
Promptly, the invention provides that a kind of manufacturing is selected from by unsaturated hydrocarbons, carbon number is that 3 and 4 unsaturated aliphatic aldehyde and carbon number are more than one the manufacture method of reaction product in the group formed of 3 and 4 unrighted acid, and this method is following (A) or method (B):
(A) supply response raw mix in possessing the plate-type reactor that is formed at the catalyst layer between the heat transfer plate, this reacting material mixture contains to be selected from by carbon number and is reaction raw materials at least a in the group formed of 3 and 4 the hydrocarbon and the tert-butyl alcohol and contains molecularity oxygen, above-mentioned reaction raw materials is carried out catalytic gas phase oxidation, make that to be selected from by unsaturated hydrocarbons and carbon number be at least a reaction product in the group formed of 3 and 4 unsaturated aliphatic aldehyde;
(B) for using the method that possesses the plate-type reactor that is formed at the catalyst layer between the heat transfer plate, wherein, the supply response raw mix, this reacting material mixture contains that to be selected from by carbon number be at least a and molecularity oxygen of the reaction raw materials in the group formed of 3 and 4 unsaturated aliphatic aldehyde, above-mentioned reaction raw materials is carried out catalytic gas phase oxidation, make that to be selected from by carbon number be at least a reaction product in the group formed of 3 and 4 unrighted acid;
Wherein, above-mentioned plate-type reactor is split into 2 different above conversion zones of average layer thickness of catalyst layer, supply with the thermal medium body that independently carries out the temperature adjustment to above-mentioned 2 above conversion zones, to carry out heat extraction across above-mentioned heat transfer plate by the heat that above-mentioned oxidation generates, and the temperature in the above-mentioned catalyst layer of independent control;
The temperature T (S1) that is supplied to the above-mentioned thermal medium body of conversion zone S1 is higher than the temperature T (S2) of the above-mentioned thermal medium body that is supplied to conversion zone S2, described conversion zone S1 approaches the inlet of above-mentioned reacting material mixture most, described conversion zone S2 is adjacent with above-mentioned conversion zone S1, and is positioned at the downstream of above-mentioned reacting material mixture stream;
To above-mentioned being selected from by carbon number is that reaction raw materials at least a in the group formed of 3 and 4 the hydrocarbon and tert-butyl alcohol load when carrying out oxidation, above-mentioned reaction raw materials is more than 150 liter per hours [converting through standard state (0 ℃ of temperature, 101.325kPa)] with respect to per 1 liter of catalyst;
To above-mentioned being selected from by carbon number is that reaction raw materials at least a in the group formed of 3 and 4 unsaturated aliphatic aldehyde load when carrying out oxidation, above-mentioned reaction raw materials is more than 160 liter per hours [converting through standard state (0 ℃ of temperature, 101.325kPa)] (hereinafter being also referred to as " the 3rd manufacture method of reaction product ") with respect to per 1 liter of catalyst.
In addition, the invention provides the 3rd manufacture method of reaction product, wherein preferably, temperature at the thermal medium body that will be supplied to not specific any conversion zone S (j) is made as T (Sj), it is adjacent with above-mentioned conversion zone S (j) to be supplied to and the temperature of above-mentioned thermal medium body of conversion zone S (j+1) that be positioned at the downstream of reacting material mixture stream when being made as T (Sj+1), and above-mentioned T (Sj) and above-mentioned T (Sj+1) satisfy the relation of T (Sj)-T (Sj+1) 〉=5.
In addition, the invention provides the 3rd manufacture method of reaction product, wherein the number of preferred above-mentioned conversion zone is 2～5, and towards outlet, the average layer thickness of the catalyst layer of each conversion zone increases by the inlet of reacting material mixture.
In addition, the invention provides the 3rd manufacture method of reaction product, wherein preferably, be that reaction raw materials at least a in the group formed of 3 and 4 the hydrocarbon and tert-butyl alcohol load when carrying out oxidation, above-mentioned reaction raw materials is 170～290 liter per hours [converting through standard state (0 ℃ of temperature, 101.325kPa)] with respect to per 1 liter of catalyst to above-mentioned being selected from by carbon number.
In addition, the invention provides the 3rd manufacture method of reaction product, wherein preferably, be that reaction raw materials at least a in the group formed of 3 and 4 unsaturated aliphatic aldehyde load when carrying out oxidation, above-mentioned reaction raw materials is 180～300 liter per hours [converting through standard state (0 ℃ of temperature, 101.325kPa)] with respect to per 1 liter of catalyst to above-mentioned being selected from by carbon number.
In addition, the invention provides the 3rd manufacture method of reaction product, is more than 90% at the conversion ratio of the reaction raw materials in the reaction product exit of above-mentioned plate-type reactor preferably wherein.
In addition, the invention provides the 3rd manufacture method of reaction product, wherein preferably, above-mentioned reaction raw materials is a propylene, and the temperature that is supplied to the thermal medium body of above-mentioned 2 above conversion zones is 320～400 ℃; Perhaps above-mentioned reaction raw materials is a methacrylaldehyde, and the temperature that is supplied to the thermal medium body of above-mentioned 2 above conversion zones is 250～320 ℃.
In first plate-type reactor, because the measured value of the distance in the plate-type reactor between the surface of heat transfer plate is included in the above-mentioned specific scope with respect to its design load, thereby can out of control reaction not controlled by the temperature control of thermal medium, even and then do not use very a large amount of artificial, a large amount of steel can make the plate-type reactor that can carry out such control yet, can access plate-type reactor more suitable aspect industrial applicibility.
In addition, in first plate-type reactor, consider from the aspect of the less plate-type reactor of the difference of the measured value of the distance between the surface that can access heat transfer plate and design load, the axial length of above-mentioned heat transfer plate be 5m following, be preferably further effect arranged below the 2m.
In addition, in first plate-type reactor, consider further have the sept that is used between above-mentioned heat transfer plate, forming appointed interval further effect is arranged from the aspect of the less plate-type reactor of the difference of the measured value of the distance between the surface that can access heat transfer plate and design load.
In addition, in first plate-type reactor, above-mentioned heat transfer plate is engaged by two steel plates and forms, these two steel plates are shaped as, a plurality of axles with heat transfer plate link to each other the cross sectional shapes of the above-mentioned heat-transfer pipe shape that forms that is divided into two, thus, consider to have further effect from the aspect of the less plate-type reactor of the difference of the measured value of the distance between the surface that can access heat transfer plate and design load.
In addition, in first plate-type reactor, the upstream side of the ventilation direction of the unstrpped gas in the gap of difference between heat transfer plate of the measured value of the distance between above-mentioned surface and above-mentioned design load is littler, considers more to produce effect from the control accuracy aspect that improves reaction; In above-mentioned raw materials gas, be that the difference of the measured value of the distance position, between above-mentioned surface below 70% and above-mentioned design load is less than greater than the measured value of distance 70% position, between above-mentioned surface and the difference of above-mentioned design load further effect being arranged in above-mentioned reactivity in the raw material reaction rate.
In addition, in first plate-type reactor, the total measurement (volume) in the gap between above-mentioned heat transfer plate is more than the 3L, makes the aspect of reaction product from high production rate ground and considers to have further effect.
In addition, in first plate-type reactor, further has temperature measuring apparatus, this temperature measuring apparatus is used to measure the temperature of the position more than 2 places of the catalyst layer that catalyst is filled in the gap between above-mentioned heat transfer plate and forms, and considers to have further effect from the aspect of the control accuracy that improves reaction.
In addition, in first manufacture method of reaction product, the reaction of the raw material in the presence of catalyst in the unstrpped gas is exothermic reaction, considers more to produce effect from the aspect that significantly obtains effect of the present invention; Above-mentioned reaction product is methacrylaldehyde and/or acrylic acid, MAL and/or methacrylic acid, maleic acid, phthalic acid, ethylene oxide, alkane, alcohol, acetone and phenol or butadiene, has the effect of more advancing one deck.
In addition, in the preparation method of first plate-type reactor, in above-mentioned heat transfer plate, use error with respect to the design load of the shaping of steel plate be ± 0.5mm is with interior shaping steel plate, from the aspect consideration of the difference that reduces measured value and above-mentioned design load further effect arranged.
In addition, in the preparation method of first plate-type reactor, across be used for forming between heat transfer plate relatively to the surface of heat transfer plate between the distance sept that becomes the interval of design load dispose heat transfer plate before engaging, from the aspect consideration of the difference that reduces measured value and above-mentioned design load further effect is arranged.
In second plate-type reactor,, can fill and the corresponding catalyst of measuring of the capacity of each section that forms by dividing plate owing to have aforementioned barriers; By the occupied state that makes catalyst in each section is constant, catalyst filling equably in the whole gaps between can the adjacent heat transfer in plate-type reactor.Thus,, compare with existing plate-type reactor for plate-type reactor of the present invention, can be evenly and easily catalyst is filled into gap between adjacent heat transfer.
In addition, in second plate-type reactor, above-mentioned 2 identical with upper curtate volume separately, consider to have further effect from the constant aspect of occupied state that is easy to make catalyst each section.
In addition, in second plate-type reactor, above-mentioned 2 is 1～100L with upper curtate volume separately, considers to have further effect from the aspect that is easy to carry out the filling operation of catalyst each section.
In addition, in second plate-type reactor, above-mentioned 2 is 2～25L with upper curtate volume separately, considers to have further effect from the aspect that is easy to carry out the filling operation of catalyst each section.
In addition, in second plate-type reactor, further have above-mentioned breather plug, consider to have further effect with the aspect that the section unit takes out, catalyst evenly and easily is filled in the gap between adjacent heat transfer and adjusts the occupied state of the catalyst the above-mentioned gap easily from the catalyst that will be filled in the gap between adjacent heat transfer.
In addition, in second plate-type reactor, have above-mentioned first fastener, above-mentioned vent board, above-mentioned skirt section and above-mentioned second fastener, consider that from the aspect that breather plug is fixed on the end of each section with full intensity and is easy to carry out the charge and discharge operations of breather plug simultaneously further effect is arranged.
In addition, in second plate-type reactor, above-mentioned 2 0.1～1m that are spaced apart with upper spacer consider to have further effect from the aspect that is easy to carry out the catalyst filling operation each section.
In recent years, chemicals is many to be produced in a large number with large-scale equipment, and the catalytic amount that to be arranged at reactor in the manufacturing equipment be maximization, inserted is also for a large amount of, in large-scale reactor evenly, catalyst filling is very important efficiently.Particularly produce or absorption reaction heat and since the temperature due to the reaction heat rise or descend to reaction speed or reaction achievement, further under the situation to the influential reaction of degradation of catalyst, make reaction raw materials and catalyst even contact such as gas and liquid, this is being a significant problem aspect more good reactor of design.
In second manufacture method of reaction product, above-mentioned raw materials is an ethene; Being selected from by carbon number is at least a in the group formed of 3 and 4 the hydrocarbon and the tert-butyl alcohol or to be selected from by carbon number be at least a in the group formed of 3 and 4 unsaturated aliphatic aldehyde; Carbon number is the hydrocarbon more than 4; Dimethylbenzene and/or naphthalene; Alkene; Carbonyls; Cumene hydroperoxide; Butylene; Or ethylbenzene, resulting above-mentioned reaction product is an ethylene oxide; Carbon number is that 3 and 4 unsaturated aliphatic aldehyde and/or carbon number are 3 and 4 unrighted acid; Maleic acid; Phthalic acid; Alkane; Alcohol; Acetone and phenol; Butadiene; Or styrene; In this manufacture method, owing to use above-mentioned plate-type reactor, therefore above-mentioned reaction raw materials so can improve the heat extraction or the heating means of reaction heat in such haptoreaction, considers on the one hand that from this further effect is arranged through evenly being filled to the catalyst treatment between heat transfer plate.
In addition, in the 3rd manufacture method of reaction product, supply response raw material in the plate-type reactor that is filled with catalyst reacts this reaction raw materials and makes product; In this manufacture method, when the processing load of the reaction raw materials that improves the unit catalyst, can prevent the increase of the pressure loss of the reacting fluid by catalyst, and can prevent heat spot by the heat that is generated by reaction is carried out suitable control, can when preventing the catalyst damage, improve the yield of goal response product.
Description of drawings
Fig. 1 is the figure that schematically shows the formation of the plate-type reactor in the one embodiment of the present invention.
Fig. 2 is the sectional view during along the plate-type reactor that A-A ' line cuts off Fig. 1.
Fig. 3 is the sectional view during along the plate-type reactor that B-B ' line cuts off Fig. 1.
Fig. 4 is the figure of an example of outward appearance that shows the plate-type reactor of Fig. 1.
Fig. 5 is the figure that shows the size of heat-transfer pipe 1.
Fig. 6 is the figure that shows an example of thermal medium mixing arrangement.
Fig. 7 is the figure that shows an example of dividing plate 7.
Fig. 8 is the figure that shows an example of breather plug 8.
Fig. 9 is the figure of an example that shows the state that is provided with of breather plug 8.
Figure 10 is the figure of an example of displays temperature determinator 9.
Figure 11 is the figure that is presented at an example of the catalyst layer that forms in the gap of 2 of heat transfer plates.
Figure 12 is the figure that schematically shows other form of heat transfer plate.
Figure 13 is the figure that schematically shows the formation of second embodiment in the plate-type reactor of the present invention.
Figure 14 is the figure in the cross section when showing along plate-type reactor that A-A ' line cuts off Figure 13.
Figure 15 is the figure in the cross section when showing along plate-type reactor that B-B ' line cuts off Figure 13.
Figure 16 shows adjacent heat transfer 2 and the figure that is located at dividing plate 7 therebetween.
Figure 17 is the figure that shows an example of dividing plate 7.
Figure 18 is the figure that shows other example of dividing plate 7.
Figure 19 is the figure that shows other example of dividing plate 7.
Figure 20 is the figure that shows other example of dividing plate 7.
Figure 21 is the figure that shows other example of dividing plate 7.
Figure 22 is the figure that shows other example of dividing plate 7.
Figure 23 is the figure that schematically shows the formation of the 3rd embodiment in the plate-type reactor of the present invention.
Figure 24 is the figure in the cross section when illustrating along plate-type reactor that A-A ' line cuts off Figure 23.
Figure 25 is the figure in the cross section when illustrating along plate-type reactor that B-B ' line cuts off Figure 23.
Figure 26 is the figure that dividing plate 7 is shown.
Figure 27 be illustrate adjacent heat transfer 2 be located at therebetween dividing plate 7 and the figure of breather plug 8.
Figure 28 is the stereogram that breather plug 8 is shown.
Figure 29 is the expanded view that breather plug 8 is shown.
Figure 30 is the figure that the free construct for handling of breather plug 8 and dividing plate 7 is shown.
Figure 31 is the figure of an example that the instrument of the dismounting that is used for breather plug 8 is shown.
Figure 32 is the figure that other free construct for handling of breather plug 8 and dividing plate 7 is shown.
Figure 33 is the figure that other example of breather plug used among the present invention is shown.
Figure 34 is the figure that other example of breather plug used among the present invention is shown.
Figure 35 is the figure that other example of breather plug used among the present invention is shown.
Figure 36 is the figure that other example of breather plug used among the present invention is shown.
Figure 37 is the figure that other example of breather plug used among the present invention is shown.
Figure 38 is the figure that other example of breather plug used among the present invention is shown.
Figure 39 is other example and the fixing figure that constitutes of its loading and unloading that breather plug used among the present invention is shown.
Figure 40 is other example and the fixing figure that constitutes of its loading and unloading that breather plug used among the present invention is shown.
Figure 41 shows the longitudinal section of plate-type reactor.
Figure 42 shows the longitudinal section of plate-type reactor.
Figure 43 shows the enlarged drawing of heat transfer plate.
Symbol description
1, a～c heat-transfer pipe
2,57 heat transfer plates
3 grip blocks
4 keep rod
5 thermal medium feedwaies
6 gas dispenser
7 dividing plates
8 breather plugs
9 temperature measuring apparatus
10,46 perforated plates
11,12 chucks
13,16,18 mouths of pipe (ノ ズ Le)
14 heat exchangers
15 pumps
17 distributing pipes
19 gateways (マ Application ホ one Le)
20 windows
21 vent boards
22 first skirt sections
23 second skirt sections
24 cards end window
25,50,51 card claw stops
26 supports
27 temperature measuring portions
28 spacer rods
29 flanges
30 connectors
31 cables (ケ one Block Le)
32 fixedly use flange
33～35 streams
36,43 catalyst layers
37～39,40～42 conversion zones
44 shells
45 thermal medium body accommodation sections
47 temperature adjustment devices
48,48 ' blow vent
49,49 ' outer casing end
52 first breather pipes
53 second breather pipes
54 flange portion
55 steady pins
56 afterburning parts
58 reaction gas inlets
59 reaction gas outlet
60-1 thermal medium body stream
60-2 thermal medium body stream
60-3 thermal medium body stream
61 thermal medium body supply ports
The interval of a pair of heat transfer plate of P
L wave period
The height of H ripple
Y represents the arrow of the mobile direction of thermal medium
X at interval
The specific embodiment
＜the first plate-type reactor 〉
First plate-type reactor has and is used to the reaction vessel that gaseous feed is reacted, the thermal medium feedway that is arranged side by side 2 above heat transfer plates in above-mentioned reaction vessel and is used for supplying with to above-mentioned heat transfer plate the thermal medium of desired temperature.
In above-mentioned reaction vessel, can use and supply with gaseous feed (unstrpped gas), discharge the container that generates gas and hold 2 above heat transfer plates side by side.Because plate-type reactor is often used in the reaction in atmosphere pressurized conditions under, thereby above-mentioned reaction vessel is preferably tolerance 3,000kPa (kPa) in the resistance to pressure container of pressure.As such reaction vessel, for example can enumerate following container etc., this container has combination and cylindrical portion or its a part of shell (shell) is arranged, utilize plate member that inside is cut apart with the shell that holds 2 above heat transfer plates and by the parts that constitute the plane inner face to surround inside with the housing shape that holds 2 above heat transfer plates.
Above-mentioned heat transfer plate comprises 2 above heat-transfer pipes that link in vertical direction with the periphery of cross sectional shape or ora terminalis.Like this, heat transfer plate is the plate body that comprises 2 above heat-transfer pipes arranged side by side.In heat transfer plate, heat-transfer pipe can directly connect, and also can connect indirectly by suitable parts such as plate or hinges.Consider that from the aspect that obtains heat transfer plate with low cost preferred heat transfer plate forms by two steel plates are engaged, these two steel plates are configured as a plurality of directly or indirectly continuous shapes of shape that the cross sectional shape with heat-transfer pipe is divided into two separately.
The interval of above-mentioned heat transfer plate is set according to design load, can also can be the different interval more than two kinds for uniformly-spaced.For example the interior shape at reaction vessel is under the situation of rectangle, and the mode that heat transfer plate can be parallel to each other according to the axle at heat transfer plate between heat transfer plate, the axle of heat-transfer pipe is parallel to each other between heat transfer plate is provided with.For example the inside of reaction vessel is under the situation cylindraceous in addition, heat transfer plate can be provided with in a manner described, also can be provided with for the mode (promptly radially) that the axle of heat-transfer pipe between the radial direction of the cross section of reaction vessel, heat transfer plate is parallel to each other according to the axle of heat transfer plate.
There is no particular restriction for the number of the heat transfer plate that is held in above-mentioned reaction vessel, determined by the required catalytic amount of reaction in practicality, is generally tens of to hundreds of.In addition, number for the heat transfer plate that is held in the above-mentioned reaction vessel, large-duty aspect from the industrial production of realization response product is considered, being preferably the total capacity that makes the gap between heat transfer plate is the above number of 3L (liter), more preferably making above-mentioned total capacity is the above number of 100L, and more preferably making above-mentioned total capacity is the above number of 250L.Insert in the gap between heat transfer plate under the situation of sept, the volume of a section that preferably is spaced apart thing and heat transfer plate and is surrounded is more than the 1L, more preferably more than the 10L.
For the axle base that is contained in the above-mentioned heat transfer plate in the reaction vessel, aspect abundant control reaction temperature the gas phase haptoreaction, consider, be preferably 10～50mm.In addition, for the axle of heat transfer plate, when observing above-mentioned heat transfer plate by above-mentioned gap, on the cross section of the heat transfer plate when the gas ventilation direction in above-mentioned gap is cut off heat transfer plate, under the situation that whole heat-transfer pipes connects in a straight line in heat transfer plate, the axle of heat transfer plate refers to this straight line, and under the out-of-line situation of the connecting portion of whole heat-transfer pipes, the axle of heat transfer plate refers to the straight line by the mid point between two parallel lines that clip whole connecting portions.
Axle base for above-mentioned heat transfer plate, from effectively removing the heat that is accompanied by reaction, prevention because the aspect of the deterioration of the catalyst due to the heat spot (under the situation of exothermic reaction) of catalyst layer is considered, the aspect that obtains high reactivity and high response energy from the whole layer of catalyst layer temperature everywhere is controlled at optimum range is considered in addition, preferably count 10～50mm (in the adjacent heat transfer 1.1～5 times of the half value sum of heat-transfer pipe width) with mean value, more preferably 10～40mm, more preferably 20～35mm.
The axle base of above-mentioned heat transfer plate to the diameter of catalyst (in industrial catalyst, be preferably 1～10mm) usually, the reactivity of catalyst, further also influential to the resistance to elevated temperatures of catalyst.Heat extraction for reaction heat, the easy more control of the more little reaction of the axle base of heat transfer plate, but and if the axle base of the heat transfer plate more than 5～10 times of non-catalytic diameter, bridge joint (Block リ Star ジ Application グ) then can take place when catalyst filling, packed density might reduce.
Above-mentioned heat transfer plate can be in above-mentioned reaction vessel be arranged according to the flange mode opposite to one another on the surface of heat transfer plate, also can be relative according to the surperficial recessed edge of the surperficial flange of side's heat transfer plate and the opposing party's heat transfer plate to mode arrange.
For above-mentioned heat-transfer pipe, when above-mentioned heat transfer plate was contained in the reaction vessel, the axle of heat-transfer pipe was configured in the direction with respect to the ventilation direction crosscut in the reaction vessel usually.At this moment, for the axle of heat-transfer pipe and the angle between the ventilation direction in the reaction vessel, as long as the axle of heat-transfer pipe is not particularly limited with respect to the ventilation direction crosscut of gas in reaction vessel.For heat-transfer pipe, consider from the aspect of the reaction of controlling raw material by the temperature of adjusting thermal medium in the heat-transfer pipe, more preferably the axle of heat-transfer pipe with respect to the flow direction of the ventilation direction quadrature in the reaction vessel, the thermal medium that promptly in heat-transfer pipe, flows with respect to the ventilation direction quadrature in the reaction vessel.
Above-mentioned heat-transfer pipe preferably forms by having the material that the conductivity of heat of heat exchange takes place between the catalyst layer that makes the thermal medium in the heat-transfer pipe and be external to heat-transfer pipe.As such material, can enumerate for example stainless steel and carbon steel, Hastelloy, titanium, aluminium, engineering plastics and copper.The preferred stainless steel that uses.In stainless steel, preferred 304,304L, 316 and 316L.The cross sectional shape of heat-transfer pipe can be circle; Can intend circular for ellipse, elliposoidal etc.; Can be leaf for what the circular arc symmetry was formed by connecting; Can be polygons such as rectangle; Also can be for these a plurality of shapes that combine.Periphery in the cross sectional shape of heat-transfer pipe is meant the periphery in the circle, and the ora terminalis in the cross sectional shape of heat-transfer pipe is meant the major axis ora terminalis intended in the circle or the edge on the one side in the polygon.
In each heat transfer plate, diameter for the axial above-mentioned heat-transfer pipe of heat transfer plate, bending resistance (anti-crawl agentdefiection) rigidity from the direction of the two quadrature of the axle of fully guaranteeing (1) and heat transfer plate and heat-transfer pipe, (2) formability of heat-transfer pipe shape and forming accuracy, (3) aspect of removing the necessary heat transfer area of reaction heat is considered, and from the flow distribution of the appropriate reacting gas of acquisition (4) and the heat transfer coefficient of catalyst layer, (5) aspect of the thermal medium flow velocity of the appropriateness in the heat-transfer pipe and heat transfer coefficient is considered, is preferably 10～100mm, 15～70mm more preferably, 20～50mm more preferably.
In addition, in each heat transfer plate, for the direction of the axle quadrature of heat transfer plate on the radius of above-mentioned heat-transfer pipe, the aspect of the reaction temperature from abundant control gas phase haptoreaction is thought of as 1.5～25mm.For the radius of above-mentioned heat-transfer pipe, control the distance between adjacent heat transfer, the angle of adjustment catalyst layer temperature accordingly from the reaction heat that produces between (1) and this heat transfer plate; Fully guarantee the necessary heat transfer area of heat extraction and the formability of (3) heat-transfer pipe shape and the angle of forming accuracy of (2) reaction heat; The flow velocity of the thermal medium in heat transfer coefficient, the loss of (5) reaction gas pressure and (6) heat-transfer pipe of disorder and the catalyst layer of the velocity flow profile of (4) reacting gas of obtaining appropriateness and the angle consideration of heat transfer coefficient are preferably 1.5～25mm, more preferably 3～20mm, 5～15mm more preferably.
In plate-type reactor, the distance between heat transfer plate is that purpose is adjusted with the temperature of control catalyst layer usually.Above-mentioned heat transfer plate axially and with the direction of axle quadrature on, heat-transfer pipe radius separately also and the particle diameter of distance between heat transfer plate and catalyst related, be can reach above-mentioned purpose in the scope of above-mentioned record by making described radius.
Need to prove, the shape and size in 2 above heat-transfer pipe cross sections separately in a heat transfer plate can be necessarily also can be different.
In addition, the length on heat-transfer pipe is axial is not specially limited, and is generally 0.5～20m.From the aspect of a large amount of production reaction products, the axial length of heat-transfer pipe is preferably 3～15m, 6～10m more preferably.
Consider from the aspect of distortion such as the deflection that prevents to be contained in the heat transfer plate in the reaction vessel, heat transfer plate axially (that is, with the cross section of the heat-transfer pipe of the axle quadrature of heat-transfer pipe on the closure of heat-transfer pipe) length be preferably below the 5m, more preferably 0.5～2m, 0.5～1.5m more preferably.
When making heat transfer plate the easiness of the plate width of cloth specification of used steel plate and acquisition for practicality and the making of heat transfer plate cheaply be very important, usually, the size of the steel plate that can obtain also is 1.5～2m or below it in the world.Therefore, under the plate width of cloth surpasses the situation of above-mentioned practical dimensions, also the steel plate more than 2 can be engaged and use, but for the formability at the junction surface of steel plate, its forming accuracy might reduce.
For the design load of the distance between the surface of realizing heat transfer plate, the error due to during steel formability is very important.Error due to during steel formability has the error of the axial sum of errors heat-transfer pipe closure of heat-transfer pipe, and they are all very important.Particularly the flow direction (being generally the closure of heat-transfer pipe) of reacting gas go up between surface between the change heat transfer plate apart from the time, the shape forming accuracy of the heat-transfer pipe on the flow direction of reacting gas is a particular importance.Consider that from the aspect that these errors is suppressed at below the desired value the axial length of heat transfer plate is preferably below the 2m.
The design load of the distance between the surface of to above-mentioned heat transfer plate is 5～50mm relatively.Distance between the surface of so-called heat transfer plate refers to herein, relatively to heat transfer plate between the gap, and the direction of equidistant the quadrature of face that form apart from axle by above-mentioned heat transfer plate on the surface of heat transfer plate between distance.Perhaps the distance between the surface of so-called heat transfer plate refers to, when when above-mentioned heat transfer plate is observed in above-mentioned gap, in the cross section of the heat transfer plate when the gas ventilation direction in above-mentioned gap is cut off heat transfer plate, and the surface of heat transfer plate on the direction of the equidistant line quadrature of axle of above-mentioned heat transfer plate between distance.When heat-transfer pipe is connected with the thermal medium feedway, for prevent thermal medium in reaction vessel spill and gas by reaction vessel to the spilling of heat-transfer pipe or thermal medium feedway, usually heat-transfer pipe is engaged with the thermal medium feedway by welding.Thereby in reaction vessel, heat transfer plate is fixed in irreversible mode usually.Therefore, the configuration of the heat transfer plate in the reaction vessel pre-determines with the design load corresponding to desired reaction achievement usually.
Above-mentioned design load can be determined based on the condition of reaction control and reaction achievement.The condition of reaction control for example can be determined based on the higher limit of the absolute value of the peak temperature of reaction time catalizer layer.The reaction achievement for example can consider that the selection rate of conversion of raw material and product mainly determines based on the productive rate of product.For above-mentioned design load, can consider the kind of catalyst, the composition of unstrpped gas and the extra factors such as temperature of flow and thermal medium, the form of the distance between the thickness of the catalyst layer when reacting the condition of controlling and satisfying the condition of reacting achievement to satisfy, the surface of heat transfer plate is tried to achieve.In addition, the peak temperature of catalyst layer is the maximum temperature of catalyst layer in exothermic reaction, is the minimum temperature of catalyst layer in the endothermic reaction.
Above-mentioned design load can be tried to achieve by following mode: based on the calculating of computer simulation; Based on the experiment of testing machine, for example, having simple plate-type reactor that constitutes such as a pair of heat transfer plate and the total saturation of catalyst are only arranged is testing machines such as small-sized plate-type reactor about 3L; Perhaps based on the experiment of pipe reaction testing machine, the chuck that this pipe reaction testing machine has a reaction tube that is filled with catalyst and makes thermal medium circulation around reaction tube.Computer simulation for example can use the CFX of ANSYS Co., Ltd., the STAR-CD of CD adapco society, the softwares such as gPROMS of PSE society to carry out.
For above-mentioned design load, from the aspect of the productivity ratio (space time yield) of the reaction product of the precision control of reaction and reaction achievement (reaction yield or selection rate), unit catalytic amount, this design load is preferably 5～50mm, more preferably 7～30mm, 10～25mm more preferably.In order to reach the high production rate of catalyst, the distance between the surface of heat transfer plate is little then to be easy to the precision control carrying out temperature control, can react, but the distance between the surface of heat transfer plate also is subjected to the restriction of the particle diameter of the catalyst that inserted.In industrial catalyst, the particle diameter of the catalyst 1～10mm that adopt more, also from the aspect of these conditions, above-mentioned design load also can carry out preferably determining in above-mentioned scope.
Relatively poor (design load-measured value) of the measured value of the distance between the surface of to above-mentioned heat transfer plate and design load be-0.6～+ 2.0mm.The above-mentioned measured value of "-" expression is less than above-mentioned design load herein, and the above-mentioned measured value of "+" expression is greater than above-mentioned design load.
Distance between the surface of above-mentioned heat transfer plate is as long as in the scope of 5～50mm, can for relatively to any position on surface of heat transfer plate between distance.For example, the heat-transfer pipe that is positioned at upstream side on will the ventilation direction in the unstrpped gas among the heat-transfer pipe that heat transfer plate comprised, in reaction vessel is during as heat-transfer pipe A, the distance between the surface of heat transfer plate can for relatively to a pair of heat transfer plate in distance between the flange that produces of heat-transfer pipe A; Also can for relatively to a pair of heat transfer plate in heat-transfer pipe A and and the adjacent heat-transfer pipe in its downstream between the recessed intermarginal distance that produces of connecting portion; Can also be the distance between recessed edge and the flange, this recessed edge be relatively to a pair of heat transfer plate in a side or the opposing party's the heat transfer plate heat-transfer pipe A and and the adjacent heat-transfer pipe in its downstream between the recessed edge that produces of connecting portion, this flange is the flange that the heat-transfer pipe A in the heat transfer plate with a opposing party or a side produces.
Distance between the surface of above-mentioned heat transfer plate for example can by insert with this surface between rod with identical thickness of the design load of distance measure.In addition, distance between the surface of above-mentioned heat transfer plate for example can followingly be tried to achieve: insert components of assays in above-mentioned gap, this components of assays has the insertion pole member that is inserted in the above-mentioned gap and measures pole member, and this mensuration pole member has the length of above-mentioned design load with the axle orthogonal configuration of inserting pole member at the front end that inserts pole member.The angle or the anglec of rotation of the axle of the insertion pole member the when surface of the heat transfer plate in the end of measuring pole member and the above-mentioned gap is contacted are measured, and are obtained by this angle thus and measure contact distance between the surface of heat transfer plate partly of pole member.
If the difference of above-mentioned measured value and above-mentioned design load greater than+2.0mm, then can not fully control reaction, suppress runaway reaction, prevent the deterioration of catalyst and prevent the reduction of reaction yield.In addition, if the difference deficiency-0.6mm of above-mentioned measured value and above-mentioned design load, then the supply in the gap of catalyst between heat transfer plate can produce obstacle, perhaps promptly allowing to does not have obstacle ground to carry out the supply of catalyst, the packed density of formed catalyst layer also can reduce, and has catalytic amount to be not enough to reach the situation of desired reactivity.From carrying out the aspect of more accurate reaction control, the difference of above-mentioned measured value and above-mentioned design load is preferably-0.5～+ 1.5mm, more preferably-0.5～+ 1.0mm, more preferably-0.3～+ 1.0mm.
In addition, although the difference of wishing above-mentioned measured value and above-mentioned design load most is in-0.6 in whole plate-type reactors～+ scope of 2.0mm in, but from not only preventing runaway reaction but also keep large-duty aspect and consider, among preferred all measured values 50% or more and the difference of above-mentioned design load be included in-0.6～+ scope of 2.0mm, more preferably all among the measured values 70% or more and the difference of above-mentioned design load be included in-0.6～+ scope of 2.0mm, further preferably be included in-0.6 with the difference of above-mentioned design load 80% or more～+ scope of 2.0mm, further preferred more than 90% and the difference of above-mentioned design load be included in-0.6～+ scope of 2.0mm.
The measuring point of above-mentioned measured value heat transfer plate axially on be preferably 2～30, more preferably 5～25, more preferably 10～20.In addition, the measuring point of above-mentioned measured value the heat-transfer pipe of heat transfer plate axially on be preferably 2～50, more preferably 5～30, more preferably 10～20.
As described later, in order to control the interval of adjacent heat transfer, between heat transfer plate, insert sept (dividing plate), sept has the effect at the interval of adjusting heat transfer plate in this case, thereby in this case, the middle position of above-mentioned measured value between sept measured 2 positions and got final product.Being provided with when 2 above septs are set is generally 50cm～1m at interval, but by using the high heat transfer plate of rigidity, try every possible means to be provided with the side plate itself that heat transfer plate is engaged with each other or manage to utilize welding method, as long as can control the distance between heat transfer plate thus, also the distance between sept can be made as more than the 1m.
Poor for above-mentioned measured value and above-mentioned design load, for example can by carry out following method make its-0.6～+ scope of 2.0mm, described method is: when the joint by two shaping steel plates forms heat transfer plate, select to use the method for error with respect to the design load of steel formability enough little (for example error be ± below the 0.5mm), shaping steel plate that precision is high; And the not enough shaping steel plate of selection precision, revise to improve the method that precision is used.About error with respect to the design load of steel formability, for example the laser type extensometer can be set on the two sides of shaping steel plate, by mobile extensometer or steel plate, can measure the displacement on shaping steel plate two sides thus, obtain the shape, its forming accuracy of shaping steel plate and with respect to the error of above-mentioned design load.
And then, with heat-transfer pipe axially on length be that heat-transfer pipe below the 10m is used for above-mentioned heat-transfer pipe, consider it is effectively from the aspect of the deflection that prevents heat-transfer pipe or heat transfer plate, from make the difference of above-mentioned measured value and above-mentioned design load be-0.6～+ the aspect consideration of 2.0mm is preferred.
The difference of above-mentioned measured value and above-mentioned design load can be single value, but the prediction reactivity when being applied to the gas phase haptoreaction, can be the different values more than 2 at heat transfer plate on axially.For example, in the gas phase haptoreaction, particularly react fierce, in the gap between the heat transfer plate of reaction that the raw material reaction rate is little, by making above-mentioned poor less than in the export department of unstrpped gas of the difference of the above-mentioned measured value of the inlet portion of unstrpped gas and above-mentioned design load, promptly the upstream side by the ventilation direction in the gap of difference between heat transfer plate that makes above-mentioned measured value and above-mentioned design load is littler, considers it is preferred from inhibitory reaction aspect out of control.
Consider from such aspect, preferably making in the raw material reaction rate is that the difference of the above-mentioned measured value of the position below 70% and above-mentioned design load is littler, more preferably making in the raw material reaction rate is that the difference of the above-mentioned measured value of the position below 60% and above-mentioned design load is littler, and further preferably making in the raw material reaction rate is that the difference of the above-mentioned measured value of the position below 50% and above-mentioned design load is littler.In addition, from above-mentioned aspect, the difference of above-mentioned locational above-mentioned measured value and above-mentioned design load with compare with the difference of above-mentioned design load at other locational above-mentioned measured value, preferably in more than the little 0.2mm of absolute value, more preferably in more than the little 0.5mm of absolute value.
In the gap between above-mentioned heat transfer plate, above-mentioned heat transfer plate axially on the raw material reaction rate to be the position of predetermined value determine with the carrying out of reaction and the relevant all conditions of conducting heat according to the composition of the kind of the distance between the surface of the temperature of the thermal medium of the cross sectional shape and the size thereof of heat-transfer pipe, the heat-transfer pipe of flowing through and flow thereof, heat transfer plate, catalyst and unstrpped gas and its flow etc., for example can be by determining based on the experiment of above-mentioned testing machine or based on the calculating that the aforementioned calculation machine is simulated.
Above-mentioned thermal medium feedway is as lower device: the above-mentioned heat-transfer pipe two ends in above-mentioned heat transfer plate engage with heat-transfer pipe, and are used for supplying with to heat-transfer pipe the device of the thermal medium of desired temperature.For above-mentioned thermal medium feedway, can utilize the common device that is used for supplying with to above-mentioned heat-transfer pipe thermal medium at plate-type reactor.The thermal medium feedway can all be supplied with the device of thermal medium for 2 above heat-transfer pipes to same direction, also can supply with the device of thermal medium round about for the other parts that the part of 2 above heat-transfer pipes is supplied with thermal medium, 2 above heat-transfer pipes to a direction.
In addition, from considering that preferred its of thermal medium feedway has the thermal medium circular chamber more than 2 that is split to form along the axial direction of crosscut heat transfer plate aspect 2 above conversion zones of catalyst layer formation along the axial of heat transfer plate.In addition, the thermal medium feedway is preferably the device that thermal medium is circulated by above-mentioned heat-transfer pipe inside and outside reaction vessel.
Further, the thermal medium feedway has the device of the temperature that is used to adjust the thermal medium that is supplied to heat-transfer pipe.As such device, for example can enumerate: be arranged in the circulation stream of thermal medium heat exchanger and in the thermal medium feedway be used for the thermal medium of above-mentioned chamber mix thermal medium mixing arrangement, the thermal medium of the thermal medium of different temperatures temperature measuring apparatus, be used to regulate the device of the flow of thermal medium.In above-mentioned thermal medium mixing arrangement, for example can use distributing pipe, be located at logical liquid plate in the thermal medium feedway and the silent oscillation blender that is commonly called static mixer, outstanding in this distributing pipe thermotropism medium supply apparatus, and thermal medium can be disperseed to be supplied in the thermal medium feedway.
As above-mentioned distributing pipe, for example can enumerate along the length direction of distributing pipe and have the distributing pipe of 2 so above fluid-through ports of slit or hole and the distributing pipe that further has the arm that has fluid-through port at tube wall.Above-mentioned distributing pipe preferably setting prolonging with respect to the direction of the flow direction quadrature of thermal medium in the thermal medium feedway, distributing pipe with arm has to be responsible for and arm, from the dispersion of the thermal medium of different temperatures, raising the efficiency and suppress the aspect of the pressure loss, preferred be responsible for and the arm one thermal medium feedway inherence that coexists is prolonged with respect to the direction of the flow direction quadrature of thermal medium and setting and according to being responsible for and the mutually orthogonal mode of outgoing direction of prolonging of arm is provided with.
In first plate-type reactor, also can further have above-mentioned other constitutive requirements in addition.As other such constitutive requirements, for example can enumerate sept, breather plug, temperature measuring apparatus and plate clamping part.
Above-mentioned sept (dividing plate) is for being used for forming the parts of appointed interval between above-mentioned heat transfer plate.The surperficial butt of preferred above-mentioned sept and heat transfer plate, and have sufficient rigidity aspect the interval that keeps heat transfer plate.In addition, under the situation that sept is formed by steel, consider that preferred above-mentioned sept be the parts of butt intermittently on the surface of the axial and heat transfer plate of heat transfer plate from the aspect of the amount of cutting down the needed steel of plate-type reactor.In addition, consider from the aspect of distortion such as the deflection that prevents heat transfer plate in the reaction vessel, preferred above-mentioned sept be heat transfer plate axially with the parts of the surperficial continuous butt of heat transfer plate.Further, filling aspect from catalyst, the aspect that is filled into the gap between heat transfer plate easily and accurately from the section that the gap between above-mentioned heat transfer plate can be divided into specified vol, with catalyst considers, preferred above-mentioned sept is not for axially allowing the parts that catalyst passes through at heat-transfer pipe.Consider from the aspect that prevents the distortion of heat transfer plate in the reaction vessel, the preferred interval thing more than axial arrangement 10 places of heat-transfer pipe or with 100～1, the arranged spaced of 000mm.As above-mentioned sept, for example can enumerate the parts of various forms such as rod, plate, piece and the dividing plate in aftermentioned second plate-type reactor.
Above-mentioned breather plug has aeration, and be as lower member: be used for can freely load and unload the inaccessible heat transfer plate in ground the gap or can freely load and unload obturation further have axial end above-mentioned section, heat transfer plate under the situation of sept, with the parts of not allowing that catalyst passes through.As such breather plug, for example can enumerate parts with vent board and latch for printed circuit, above-mentioned vent board obturation heat transfer plate axially on heat transfer plate between the gap or the end of above-mentioned section, above-mentioned latch for printed circuit is located on this vent board, and can freely only block with above-mentioned heat transfer plate or above-mentioned sept with loading and unloading.Aspect the gap catalyst filling between heat transfer plate easily and accurately, consider that preferred above-mentioned breather plug for being configured in the parts of the end of above-mentioned section with freely loading and unloading.Above-mentioned breather plug can use the breather plug in aftermentioned second plate-type reactor.
The said temperature determinator is a device of measuring the temperature of the catalyst layer that is formed at the gap between above-mentioned heat transfer plate.As such temperature measuring apparatus, can enumerate the device that comprises the temperature measuring portion that has flexual support and supported by this support.As above-mentioned support, can use to have flexual rope, band, chain, pipe.In addition, as the said temperature determination part, can enumerate for example platinum temperature detecting resistance body, thermistor, thermocouple and optical-fiber type temperature measuring device.
Consider that from the aspect of the temperature of holding catalyst layer the number that is provided with of said temperature determinator is preferably 2～20 in each reaction vessel.In addition, the thickness (wide) of preferred support is 0.5～5mm.Further, consider from the aspect that the temperature measuring that makes catalyst layer is reflected in the control of reaction, 1～30 temperature measuring portion preferably is set in a support, be formed with at catalyst layer under the situation of 2 above conversion zones, preferably 1～10 temperature measuring portion be set with respect to a conversion zone.For the said temperature determinator, in the gap between above-mentioned heat transfer plate, be set as linearity by on the equidistant position of distance adjacent heat transfer, above-mentioned support being opened, open under the state of establishing at above-mentioned support catalyst is filled in the above-mentioned gap, can in above-mentioned gap, suitably be configured thus.Owing to due to the form error of the distortion of heat transfer plate, heat-transfer pipe partial reaction is reached the purpose of the unusual influence of the Temperature Distribution of catalyst layer unusually, the temperature measuring position need be more than 2 places in a catalyst layer from detecting.From reacting the angle of the easiness of controlling, preferred temperature measuring position is many places.
Above-mentioned plate clamping part is at least along the ventilation with shielding unstrpped gas of the heat transfer plate that axially is connected to the two ends on the above-mentioned heat transfer plate direction side by side of heat-transfer pipe, with the parts at heat transfer plate above-mentioned 2 the above heat transfer plates of direction clamping side by side.The plate clamping part can be arranged in the reaction vessel, also can constitute reaction vessel relatively to a pair of wall.The aspect of the formation of the delay portion of the gas from the wall that prevents reaction vessel is considered, preferred plate clamping part.As such plate clamping part, can enumerate, on at least one heat-transfer pipe in the heat transfer plate at the two ends on above-mentioned 2 above heat transfer plates direction side by side, with the maintenance rod that prolongs a pair of grip block that the whole heat-transfer pipes on the outgoing direction connect and connect such grip block and keep of heat-transfer pipe.
Further, from to carry out the aspect of inching with the interval of the heat transfer plate of clamping, from being provided with easily that catalyst is filled or the aspect of scaffold (sufficient field boundary) during the inspection of plate-type reactor inside and consider into the aspect of the plate-type reactor of other condition from migrating, more preferably keep rod for example at least leading section have can twist the screw of buckling nut excellent such, can be with predetermined interval with grip block at the relative parts that on direction, connect.
In first plate-type reactor, this plate-type reactor is being used under the catalytic situation of gas phase the gap catalyst filling between above-mentioned heat transfer plate.Above-mentioned catalyst is selected according to catalytic raw material of gas phase and reaction product.Above-mentioned catalyst can use the common granular catalyst in the gap that is filled between pipe or heat transfer plate in the gas phase haptoreaction.Catalyst can for a kind of also can be for two or more.As such catalyst, for example can enumerating, particle diameter (major diameter) is the catalyst of 1～20mm.The particle diameter of employed catalyst is 1～10mm more preferably.In addition,, known shape be can use, spherical, cylindric, Raschig ring shape, saddle for example can be enumerated as the shape of catalyst.
First manufacture method of＜reaction product 〉
First plate-type reactor has heat-exchange capacity, can be used for using the exothermic reaction that needs hot-swap feature in reactor or the endothermic reaction of the gas phase haptoreaction of unstrpped gas and solid catalyst.Promptly, first plate-type reactor can be used for first manufacture method of following reaction product: this method comprises to above-mentioned reaction vessel to be supplied with gaseous feed and makes it by the operation of above-mentioned catalyst layer and the operation of supplying with the thermal medium of predetermined temperature in 2 above heat-transfer pipes that constitute above-mentioned heat transfer plate, and in the presence of above-mentioned catalyst unstrpped gas is reacted to generate the vapor reaction product.Such manufacture method can similarly be carried out with the gas phase haptoreaction of using known plate-type reactor, perhaps can carry out under same condition with the gas phase haptoreaction of using known multi-tubular reactor.
As the above-mentioned gas phase haptoreaction that is attended by exothermic reaction, for example can enumerate: generate methacrylaldehyde and/or acrylic acid reaction by propane, propylene and oxygen; Generate the reaction of MAL and/or methacrylic acid by isobutene and oxygen; Generate the reaction of ethylene oxide by ethene and oxygen; By carbon number is that to generate carbon number be 3 the unsaturated aliphatic aldehyde and/or the reaction of unrighted acid for 3 hydrocarbon and oxygen; By carbon number is that to generate carbon number be 4 the unsaturated aliphatic aldehyde and/or the reaction of unrighted acid for 4 hydrocarbon and/or the tert-butyl alcohol and oxygen; By carbon number is that 3 or 4 unsaturated aliphatic aldehyde and oxygen generate the reaction that carbon number is 3 or 4 unrighted acid; By carbon numbers such as normal butane, benzene is the reaction that hydrocarbon more than 4 and oxygen generate maleic acid; Reaction by dimethylbenzene and/or naphthalene and oxygen generation phthalic acid; Generate the reaction of butadiene by the oxidative dehydrogenation of butylene.
As the above-mentioned gas phase haptoreaction that is attended by the endothermic reaction, the dehydrogenation that for example can enumerate by ethylbenzene generates cinnamic reaction.
First manufacture method of reaction product can suitably be used for the manufacturing of MAL and/or methacrylic acid, methacrylaldehyde and/or acrylic acid, maleic acid, phthalic acid, ethylene oxide or butadiene.
For example, for first manufacture method of making (methyl) methacrylaldehyde (methacrylaldehyde or MAL) and/or (methyl) acrylic acid reaction product, except use first plate-type reactor as reactor, can be by the known method that propane, propylene or isobutene carry out oxidation being carried out as use molecularity oxygen of putting down in writing in the TOHKEMY 2003-252807 communique in the presence of catalyst or the gas that contains molecularity oxygen.In addition, the well-known catalysts in generating (methyl) acrylic acid gas phase contact oxidation, used of above-mentioned catalyst Mo-V-Te system complex oxide catalyst, Mo-V-Sb system complex oxide catalyst, Mo-Bi system complex oxide catalyst and the Mo-V system complex oxide catalyst etc. that can utilize known usage to use to put down in writing in the above-mentioned communique.
In addition, first manufacture method of reaction product can compatibly be used in following gas phase haptoreaction, and this gas phase haptoreaction is attended by exothermic reaction as the reaction of the raw material in the unstrpped gas in the presence of catalyst.
In first manufacture method of reaction product, thermal medium is supplied to heat-transfer pipe by the thermal medium feedway, and the temperature of this thermal medium is that to make peak temperature in the axial Temperature Distribution of the heat transfer plate of reaction time catalizer layer be the temperature of setting value of the peak temperature of the catalyst layer that sets when design of first plate-type reactor.The temperature control example of such thermal medium is carried out as utilizing based on the known control methods such as FEEDBACK CONTROL of above-mentioned design load.The temperature control of the thermal medium when preferably reacting is so that the peak temperature of catalyst layer is ± 20 ℃ with respect to above-mentioned design load, more preferably carry out above-mentioned control so that the peak temperature of catalyst layer is ± 10 ℃ with respect to above-mentioned design load, further preferably carry out above-mentioned control so that the peak temperature of catalyst layer is ± 5 ℃ with respect to above-mentioned design load.Experiment when the above-mentioned design load of plate-type reactor is determined in above-mentioned setting value utilization is tried to achieve, and perhaps determines in based on the calculating of aforementioned calculation machine simulation.In addition, the temperature controlling of thermal medium can utilize above-mentioned thermal medium feedway to carry out.
The preparation method of＜the first plate-type reactor 〉
First plate-type reactor be by so that relatively the distance between the surface of to above-mentioned heat transfer plate be the above-mentioned heat transfer plate of arranged spaced of above-mentioned design load, and above-mentioned heat-transfer pipe and above-mentioned thermal medium feedway utilization welding etc. engaged obtain.Above-mentioned heat transfer plate for example can be by across the thickness pole member identical with above-mentioned design load and heat transfer plate arranged side by side, thereby is configured with the interval that reaches above-mentioned design load.Above-mentioned pole member is taken out by the gap between heat transfer plate after the engaging of heat-transfer pipe and thermal medium feedway.
Perhaps, have at plate-type reactor under the situation of above-mentioned sept, above-mentioned heat transfer plate can alternately more thickly dispose by heat transfer plate before will engaging and sept, thereby is configured with the interval that reaches above-mentioned design load.
Use accompanying drawing to be described more specifically embodiments of the present invention below.
＜the first embodiment 〉
For example as Fig. 1～shown in Figure 4, first plate-type reactor has as lower member: 2 above heat transfer plates 2, and these 2 above heat transfer plates 2 are arranged side by side in above-mentioned reaction vessel, and have heat-transfer pipe 1; A pair of grip block 3, this a pair of grip block 3 at least along the axle of heat-transfer pipe 1 and heat transfer plate 2 side by side the heat transfer plate 2 at the two ends on the direction connect, and heat transfer plate 2 side by side on the direction clamping 2 above heat transfer plates 2; Keep rod 4 more than 2, this keeps excellent 4 these grip blocks 3 are coupled together more than 2; Thermal medium feedway 5, the two ends of the heat-transfer pipe 1 on this thermal medium feedway 5 and the heat transfer plate 2 connect, and supply with thermal medium to heat-transfer pipe 1; Gas dispenser 6, this gas dispenser 6 covers the two ends of 2 above heat transfer plates 2 on the direction of the axle of crosscut heat-transfer pipe 1, and makes gas in the circulation of the gap of 2 of adjacent heat transfer; Dividing plate 7, this dividing plate 7 are divided into the gap of 2 of adjacent heat transfer along the ventilation direction of gas 2 of the catalyst that holds to be filled with upper curtate; The breather plug 8 of the lower end of inaccessible each section; Temperature measuring apparatus 9, this temperature measuring apparatus 9 is provided with to the direction tensioning of the axle of crosscut heat-transfer pipe 1 at the central portion of predetermined segment; And perforated plate 10, this perforated plate 10 is provided with according to the mode of the top that covers 2 above heat transfer plates 2.
Heat-transfer pipe 1 for example be heat transfer plate 2 axially on diameter (major diameter, L) be 30～50mm, (minor axis H) is 10～20mm at the diameter with the direction of the axial quadrature of heat transfer plate 2; Cross sectional shape is with circular arc, elliptic arc, rectangle and the polygonal part pipe as the shape of main constitutive requirements.The length of heat-transfer pipe 1 is generally 0.1～20m, for example for 10m.Fig. 5 show with the circular arc be cross sectional shape constitutive requirements, cross sectional shape is leaf heat-transfer pipe.Among Fig. 5, the major diameter of heat-transfer pipe with L represent, minor axis represents with H.
Heat transfer plate 2 has the shape that 2 above heat-transfer pipes 1 link with the ora terminalis of cross sectional shape.Heat transfer plate 2 is to be welded to be bonded with each other by the flange with the end that is formed at the arc in two steel plates by two steel plates (this steel plate forms according to the mode that elliptic arc forms continuously) to form.Above-mentioned steel plate used thickness be 2mm following, be desirably the following steel plate of 1mm.Shape to the above-mentioned steel plate after being shaped is carried out close examination, for example, error with respect to the shaping design load can directly be used with interior shaping steel plate for ± 1%, can revise the error that makes with respect to the shaping design load with respect to the error of shaping design load above ± 5% shaping steel plate is in ± 2%, and then uses.
In addition, adjacent heat transfer 2 can according to the flange on surface toward each other to mode come side by side, but in the plate-type reactor of Fig. 1, according to the recessed edge on the flange on the surface of a side heat transfer plate 2 and the surface of the opposing party's heat transfer plate 2 relative to mode come side by side.
Heat transfer plate 2 can all be made of same heat-transfer pipe 1, also can be made of the different heat-transfer pipe 1 of sectional dimension.For example heat transfer plate 2 can be made of top, middle part and the bottom of heat transfer plate 2 respectively three kinds of different heat-transfer pipes of sectional dimension.More particularly, as shown in Figure 7, heat transfer plate 2 can form according to three kinds of heat-transfer pipes major axis configuration mode in a straight line separately, for example, for the top of heat transfer plate 2,20% the part that accounts for height of heat transfer plate 2 is made of the heat-transfer pipe a of sectional dimension maximum; For the middle part of heat transfer plate 2,30% the part that accounts for height of heat transfer plate 2 is made of second largest heat-transfer pipe b of sectional dimension; For the bottom of heat transfer plate 2,40% the part that accounts for height of heat transfer plate 2 is made of the heat-transfer pipe c of sectional dimension minimum; 10% the part that accounts for height of heat transfer plate 2 can be formed by the upper end of heat transfer plate 2 and the joint board of bottom.The cross sectional shape of heat-transfer pipe a for example is that major diameter (L) is leaf for 20mm's for 50mm, minor axis (H), the cross sectional shape of heat-transfer pipe b for example is that major diameter (L) is leaf for 16mm's for 40mm, minor axis (H), and the cross sectional shape of heat-transfer pipe c for example is that major diameter (L) is leaf for 10mm's for 30mm, minor axis (H).
For heat transfer plate 2, be generally 0.5～10m in the axial length of heat transfer plate 2, be preferably below the 2m.Under the axial length of heat transfer plate 2 is situation more than the 2m, 2 heat transfer plates 2 can be engaged or be used in combination.
As shown in Figures 2 and 3, grip block 3 is a pair of plate, for example a pair of plate of making for stainless steel.Grip block 3 forms greatlyyer than heat transfer plate 2, passing through to keep excellent 4 combinations in edge portion.
As shown in Figure 3, keep rod 4, for example have the stainless steel rod of screw for both ends for connecting the rod more than 2 that a pair of grip block 3 connects.As Fig. 2～shown in Figure 4, utilize nut to be fixed on the heat-transfer pipe 1 (position that above-mentioned heat-transfer pipe periphery a) is joined with heat transfer plate 2 tops at the both ends that keep rod 4 grip block 3.For grip block 3, in the scope that length is set of the screw that keeps rod 4, can on the direction of clamping heat transfer plate 2, change the position and fix.In addition, for keeping rod 4, on above-below direction, be configured in and in position that the dividing plate that the gap disposed 7 of 2 of heat transfer plates coincides.A pair of grip block 3 and maintenance rod 4 constitute above-mentioned plate clamping part.
As depicted in figs. 1 and 2, thermal medium feedway 5 is a pair of containers that the two ends with the heat-transfer pipe 1 of heat transfer plate 2 join, and it for example has as lower member: have a pair of stainless steel chuck 11,12 with the heat-transfer pipe 1 corresponding peristome that joins; Be located at the supply that is used for thermal medium on the chuck and the mouth of pipe 13 of discharge; Be used to adjust the heat exchanger 14 of the temperature of the thermal medium of discharging by chuck 11; And be used to pump 15 that thermal medium is circulated between chuck 11 and heat exchanger 14.Seals such as fixed part that thermal medium feedway 5 use screw and nuts etc. are common and packing ring are at the side edge part and the grip block 3 mutual airtight joints of grip block 3.
The inside of chuck 11,12 can be along the direction of the axle of crosscut heat transfer plate 2 being communicated with or the mode of shielding is suitably cut apart, thereby in the heat-transfer pipe 1 of every specific radical, thermal medium flows to a direction or rightabout, and thermal medium 11,12 of chucks back and forth.
In addition, thermal medium feedway 5 is for example can be shown in the arrow Y among Fig. 2 such be thermal medium in whole heat-transfer pipe 1 by side's chuck 11 to the opposing party's chuck 12 folk prescriptions to the device that flows.
Further, for thermal medium feedway 5, for example can be in chuck 11,12 or the chamber more than 2 that forms of the axial shield in chuck 11,12 with respect to heat transfer plate 2 in chamber arbitrarily in have the thermal medium mixing arrangement.As shown in Figure 6, the thermal medium mixing arrangement has and is communicated with the chuck inside and outside mouth of pipe 16 and distributing pipe 17, and this distributing pipe 17 is connected with the mouth of pipe 16 in that chuck is inner, and prolongs on the direction with respect to the flow direction quadrature of the thermal medium in the chuck.Distributing pipe 17 is for example spreading all over the pipe that is provided with the hole more than 2 on the whole length direction of distributing pipe for front end is blocked.
Gas dispenser 6 for example can be made of following reaction vessel cover and following gas vent (mouth of pipe 18), the covering that the end parts of the hood-shaped one-tenth of this reaction vessel and above-mentioned 2 above heat transfer plates is left, and the two ends of the sidewall of airtight above-mentioned thermal medium feedway and the formed reaction vessel of plate clamping part; This gas vent (mouth of pipe 18) is base feed gas or discharges the blow vent that reaction generates gas.Above-mentioned reaction vessel cover can use the cover of different shapes such as semi-spherical shape, cone shape, rectangular pyramid shape, triangular prism shape, housing.In addition, above-mentioned blow vent can use the mouth of pipe and the common blow vent that is formed at the flange of its end that for example has in the upper shed of reaction vessel cover.Above-mentioned reaction vessel cover is provided with a pair of usually with respect to the sidewall of above-mentioned reaction vessel, they can be the same or different.In addition, above-mentioned blow vent is provided with one usually on the reaction vessel cover, but also can be provided with more than 2.Further, above-mentioned blow vent is provided with a pair of usually in plate-type reactor, and they can be the same or different.
More particularly, as shown in figures 1 and 3, gas dispenser 6 is a pair of parts, and the following ora terminalis of these a pair of parts ora terminalis and grip block 3 on ora terminalis on the grip block 3 and chuck 11,12 and the lower end edge of chuck 11,12 for example use respectively that said fixing parts and seal engage airtightly to cover the two ends of 2 above heat transfer plates 2.Gas dispenser 6 for example is the stainless steel lid of semicylinder (か ま Pot こ) type.Gas dispenser 6 has the mouth of pipe 18 and gateway 19 respectively.The mouth of pipe 18 of the gas dispenser 6 by a side, gas is supplied with towards the gap of 2 of heat transfer plates, and the mouth of pipe 18 of the lid by the opposing party goes out gas from above-mentioned interstitial row.In above-mentioned plate-type reactor, grip block 3, thermal medium feedway 5 and gas dispenser 6 form reaction vessel by engaging airtightly.
Gateway 19 for operator under the state that is provided with gas dispenser 6 with respect to the gas dispenser 6 used switch door of coming in and going out.The configuration of the mouth of pipe 18 and gateway 19 is not particularly limited, and is that for example as shown in Figure 1, the mouth of pipe 18 is located at an end of lid under the situation of lid of the semicolumn bodily form in gas dispenser 6, and the other end of lid is located in gateway 19.Further, for gas dispenser 6, when sharply rising or the Security Countermeasures during abnormal response, not shown safety devices such as safety valve or fracture plate are set at the main body or the mouth of pipe 18 of the gas dispenser 6 of inlet portion and/or export department as pressure anomaly.In addition, gas dispenser 6 and gateway 19 about the reactor outlet side, can make under the situation that object decomposes or accessory substance is accumulated that is generated in the gas generation delay that contains reaction product, preferably be provided for reducing the structure or the additives of delay portion.
Dividing plate 7 along the direction of the axle of crosscut heat-transfer pipe 1, be that the ventilation direction of gas in the plate-type reactor is set between the adjacent heat transfer 2.As shown in Figure 7, dividing plate 7 for example is and the plate-shaped member surperficial butt, that have sufficient rigidity of heat-transfer pipe 1 that it has the window 20 as the rectangle through hole in the bottom.Dividing plate 7 is with the distance maintaining of heat transfer plate 2 sept at appointed interval.Dividing plate 7 can be provided with same intervals in plate-type reactor integral body, also can be provided with different interval.Dividing plate 7 for example is set up in parallel with the same intervals of 400mm, and form the 12L volume in the gap of 2 of heat transfer plates 2 with upper curtate.
As shown in Figure 8, breather plug 8 have the vent board 21 of the rectangle identical with the cross sectional shape of each section, by hang down downwards first skirt section 22 of establishing and of the minor face of vent board 21 by vertical downwards second skirt section 23 of establishing, the long limit of vent board 21.The card that forms rectangles in first skirt section 22 ends window 24 and and is located at the card claw stop 25 on its next door.
Vent board 21 for example is the plate that forms the circular port of 2mm with aperture opening ratio 30%.Card ends window 24 and forms to have width and the size highly of holding card claw stop 25.In addition, card claw stop 25 with from two parallel groovings of the following ora terminalis in first skirt section 22 laterally bent tabs form.Relatively to a pair of first skirt section 22 in, a side card end window 24 and the opposing party's card claw stop 25 relative to a, side card claw stop 25 and the opposing party's card end window 24 relative to.The window 20 of dividing plate 7 comprises simultaneously according to having that card ends the width of window 24 and card claw stop 25 and the size of height forms.
Breather plug 8 upwards inserts each section vent board 21 from the lower end of each section.Block laterally afterburning of claw stop 25 opposing this moment and press to dividing plate 7, when arriving window 20, as shown in Figure 9, discharge and enter window 20, be limited to window 20 from the extruding of dividing plate 7.
For temperature measuring apparatus 9, for example as shown in Figure 2, in heat transfer plate 2 formed gaps more than 2, be located at outermost gap and by comparison in inboard any gap.In addition, for temperature measuring apparatus 9, in a gap of 2 of heat transfer plates, along heat-transfer pipe 1 axially, be the flow direction of thermal medium, be arranged near the inlet that comprises thermal medium and near a plurality of positions the outlet.The position is set determines according to the temperature difference between the thermal medium in the thermal medium of heat-transfer pipe 1 a middle and upper reaches side of heat transfer plate 2 and downstream of temperature measuring apparatus 9.When for example the temperature of thermal medium was controlled with 0.5 ℃ unit, it was position more than 2 ℃ that temperature measuring apparatus 9 is arranged on temperature difference between the thermal medium in the thermal medium of upstream side of a heat-transfer pipe 1 of heat transfer plate 2 and downstream.
As shown in figure 10, temperature measuring apparatus 9 has: have flexual support 26; Be supported the temperature measuring portion 27 more than 2 that body 26 is supported; Prolong the spacer rod more than 2 28 that and join with the surface of heat transfer plate 2 to horizontal direction by support 26; Be located at the flange 29 of the cardinal extremity of support 26; The connector 30 that is connected with flange 29; The cable 31 that is connected with connector 30; And the fixing flange 32 of using of being located at the front end of support 26.
Support 26 is that the average thickness of tube wall is the stainless steel tubulation of 0.2mm.In support 26, insert 11 thermocouples as temperature measuring portion 27.Each temperature measuring portion 27 is configured according to the variations in temperature in each catalyst layer.For example temperature measuring portion 27 is arranged near the inlet of reacting gas in the catalyst layer, near the outlet and the position, three places that is predicted as in each conversion zone of each catalyst layer maximum temperature separately.More particularly, as shown in figure 10, on the ventilation direction in each gap, temperature measuring portion 27 is provided with one respectively, is provided with three, is provided with three, is provided with three on the top of the 3rd conversion zone that is formed by heat-transfer pipe c, is provided with one in the bottom in each gap at the central portion of being organized second conversion zone that forms by heat-transfer pipe b at the central portion of being organized first conversion zone that forms by heat-transfer pipe a in the upper end in each gap.
In addition, the temperature difference of thermal medium is that the position that reaches maximum temperature in the position more than 2 ℃ and each conversion zone that is predicted as each catalyst layer can be determined based on the experimental result of the testing machine that uses this reactor or based on the computer simulation results of the softwares such as gPROMS of the STAR-CD of the CFX that uses ANSYS Co., Ltd., CD adapco society, PSE society in each heat-transfer pipe 1.
Spacer rod 28 is fixed on the support 26 for cardinal extremity and prolongs the stainless steel bar that to horizontal direction.Spacer rod 28 has the length corresponding to the position in the support 26, and support 26 has the surperficial contacted length of the front end and the heat transfer plate 2 of spacer rod 28 when being supported in the median plane in each gap.Spacer rod 28 is provided with three from the central portion of support 26 to base end part, according to alternately with relative to the mode of each heat transfer plate 2 contacts be provided with.
For flange 29, flange 29 is supported on the flange holding components of the predetermined height in the reaction vessel in order support 26 to be fixed on the top of reaction vessel, for example it to be positioned in.The flange holding components is for example for inserting the hang down bolts established and remain on the parts of predetermined altitude by nut of logical gas dispenser 6 by upside, for example by two steel wires of clamping support 26, have the nut that hole and the steel wire holding components of supporting two steel wires that bolt uses and the steel wire holding components that will insert above-mentioned bolt in the hole that bolt is used screw on from the bottom and constitute.Fixing plectane or the wheel that with flange 32 is the diameter that had greater than the diameter in the hole in the vent board 21 of breather plug 8 for example makes above-mentioned hole that the front end of support 26 leads to vent board 21 be fixed on the front end of support afterwards.
In the temperature measuring apparatus 9 of Figure 10, in vertical direction, the bottom in above-mentioned gap, apart from each heat transfer plate 2 equidistant position, the front end of support 26 is fixed on the breather plug 8 with flange 32 by fixing; And,, utilize the fixedly cardinal extremity of support 26 of above-mentioned flange holding components apart from each heat transfer plate 2 equidistant position in the upper end in above-mentioned gap.By tightening the nut of flange holding components, nut is moved upward, and support 26 stretches upward by the flange holding components, each spacer rod 28 with the surperficial state of contact of heat transfer plate 2 under linearly.
In above-mentioned plate-type reactor, by above-mentioned formation, heat transfer plate 2 is the uniformly-spaced arranged side by side of 14mm (axle base of each heat transfer plate 2 is 30mm) with the beeline between the outer wall of heat-transfer pipe a for example.
For heat transfer plate 2, by heat transfer plate 2 and sept 7 alternate configurations are configured in desired position, in the two ends and chuck 10,11 solder joints of this position heat-transfer pipe 1.Herein, distance between the surface of heat transfer plate 2 is: when observing heat transfer plate 2 by the gap of 2 of heat transfer plates (Fig. 1), on the cross section (Fig. 3 and Fig. 5) of the heat transfer plate 2 in above-mentioned gap when the ventilation direction (B-B ' line among Fig. 1) of gas is cut off heat transfer plate 2, and be positioned at distance between the surface of the heat transfer plate 2 on the direction of the equidistant line quadrature of axle of heat transfer plate 2.Heat transfer plate 2 according to heat transfer plate 2 the axle vertically, heat-transfer pipe 1 the axle along continuous straight runs mode be configured, thereby for example for the design load of the distance between the surface of heat transfer plate 2, be in the heat transfer plate 2 that is configured of vertical direction according to axle, among the distance between the surface of heat transfer plate 2 in the horizontal direction, count 20mm with the flange of side's heat transfer plate and the recessed intermarginal distance of the opposing party's heat transfer plate, when the measured value of above-mentioned distance was 19.5～21mm, this moment, the difference with respect to the design load of the distance between the surface of heat transfer plate 2 was-0.5～1.0mm.
Catalyst filling in each section in the gap of 2 of adjacent heat transfer.Catalyst for example use maximum average grain diameter as 5mm, be shaped as the annular molybdenum (Mo)-bismuth (Bi) series catalysts.In the section that forms by heat transfer plate 2 and dividing plate 7, the catalyst of the corresponding predetermined volume of volume of filling and this section.
The state that is filled with catalyst in the gap of 2 of heat transfer plates as shown in figure 11.As shown in figure 11, for heat transfer plate 2, be circular arc or elliptic arc, rectangle or a polygonal part with 2 sheet formings, toward each other to joint, form the stream 33,34,35 of three kinds of different thermal mediums of sectional area.The width maximum of stream 33, so the width of catalyst layer 36 is the narrowest between stream 33.The flow path width of stream 34,35 reduces successively than stream 33, so the width of catalyst layer 36 broadens successively.
Three conversion zones 37,38,39 that catalyst layer 36 forms corresponding to stream 33,34,35.If the thickness that makes catalyst layer 36 for and the mean value of the distance of 2 of the heat transfer plates of the rectangular direction of axle of heat transfer plate 2, then the thickness of the catalyst layer 36 in the conversion zone 37 for example is 8～15mm, the thickness of the catalyst layer 36 in the conversion zone after conversion zone 37 38 for example is 10～20mm, and the thickness of catalyst layer 36 for example is 15～30mm in the conversion zone after conversion zone 38 39.
State plate-type reactor in the use and carry out under the catalytic situation of gas phase, reaction temperature is controlled by the temperature of the thermal medium of the heat-transfer pipe 1 of flowing through.The temperature of thermal medium is according to the difference of raw material, product, catalyst type and difference is preferably 200～600 ℃ usually.As an example of heat medium temperature, when reaction raw materials gas was C3～C4 unsaturated hydrocarbons, heat medium temperature was 300～400 ℃.The temperature that is supplied to the thermal medium of each conversion zone is determined independently of one another, is controlled.When reaction raw materials gas is (methyl) methacrylaldehyde, select the temperature of thermal medium 250～320 ℃ scopes.
The reaction conversion ratio of reaction raw materials gas is a particular importance, in order to obtain desired conversion ratio the temperature of thermal medium is controlled.When turning round, plate-type reactor, then can produce the problems such as the increase that underspeeds of catalyst activity reduction, selection rate reduction, activity or selection rate if the temperature of catalyst layer is more than the allowable temperature.So-called herein " conversion ratio " be meant, with respect to the quantity delivered of the unstrpped gas that is supplied to catalyst layer (for example propylene), is converted into the ratio of amount of the unstrpped gas of product by reaction; So-called " selection rate " be meant, the amount of unstrpped gas that is converted to the target product is with respect to the ratio of the amount of the unstrpped gas that transforms by reaction.
For the conversion ratio that obtains being scheduled to, temperature to thermal medium is controlled, but in order to keep the high-performance of catalyst for a long time, the maximum temperature of catalyst layer is to be very important below the maximum permissible temperature of employed catalyst, and it is very important more preferably in the scope that obtains desired reaction achievement the maximum temperature of catalyst layer being remained on low temperature as far as possible.
Conversion zone 2～5 supply with thermal medium so that the peak temperature of catalyst layer is above-mentioned setting value ± 10 ℃ with interior temperature respectively, and thermal medium flows in the direction rectangular with the flow direction of reacting gas (cross flow direction).Inlet is preferably 0.5～10 ℃, more preferably 2～5 ℃ with the temperature difference of exit thermal medium in a heat-transfer pipe 1.In form shown in Figure 11, the situation of the thermal medium that is controlled at predetermined temperature individual flow in each root separately of the heat-transfer pipe 1 in the stream 33～35 is for example arranged, and situation about flowing simultaneously in whole heat-transfer pipes 1 of same conversion zone is also arranged.In addition, also the thermal medium that is supplied to the heat-transfer pipe 1 of certain conversion zone and discharges can be supplied to the heat-transfer pipe 1 of same or other conversion zone.
As with the possibility height that is associated of reaction achievement, the making precision that it should be noted that of plate-type reactor, be the thickness of heat-transfer pipe a～c that the thickness (distance between the surface of heat transfer plate 2) of catalyst layer 36 is determined and the axle base of 1 pair of heat transfer plate 2.The axle base of heat transfer plate 2 is constant, the thickness of heat-transfer pipe 1 is with respect to setting value under the thin situation, perhaps if the axle base of heat transfer plate 2 is excessive with respect to setting value, then the thickness of catalyst layer 36 (distance between the surface of heat transfer plate 2) becomes big, giving and accepting of heat can not be carried out effectively, the temperature of catalyst layer 36 or reaction raw materials can not be correctly kept.
The axle base of heat transfer plate 2 is constant, the thickness of thermal medium stream is with respect under the excessive situation of setting value, perhaps if the axle base of heat transfer plate 2 is too small with respect to setting value, then the thickness of catalyst layer 36 (distance between the surface of heat transfer plate) diminishes, giving and accepting of heat becomes efficient, but can not correctly fill the catalyst of setting, can not correctly keep the gas phase haptoreaction.
In above-mentioned plate-type reactor, for thermal medium, 345 ℃ thermal medium for example flows in heat-transfer pipe 1, and the gas that will contain propylene, molecularity oxygen, steam and inert gas as unstrpped gas is mobile from the gas dispenser 6 of upside, obtains containing methacrylaldehyde and acrylic acid reacting gas thus.Quantity delivered base feed gas with the unstrpped gas of the reaction product of the desired yield that is used to obtain determine by above-mentioned design load, with temperature and quantity delivered thermal medium is supplied to heat-transfer pipe 1, utilizes temperature measuring apparatus 9 to measure maximum temperature (peak temperature) A of catalyst layers 36 by the definite thermal medium of above-mentioned design load.
Peak temperature A be above-mentioned setting value ± 10 ℃ with under the interior situation, thermal medium is supplied to heat-transfer pipe 1 with the design temperature and the quantity delivered of thermal medium.Peak temperature A is higher than under the situation of above-mentioned setting value+10 ℃, and thermal medium is supplied to heat-transfer pipe 1 with the temperature of the design temperature that is lower than thermal medium and the setting quantity delivered of thermal medium.Peak temperature A is lower than under the situation of above-mentioned setting value-10 ℃, and thermal medium is supplied to heat-transfer pipe 1 with the temperature of the design temperature that is higher than thermal medium and the setting quantity delivered of thermal medium.By control the temperature of thermal medium according to the peak temperature of catalyst layer 36, can and not reduce under the situation of reaction yield thus, make reaction product continuously in the quantity delivered that does not change unstrpped gas.
In above-mentioned plate-type reactor, owing to use the error that will be configured as to engage the heat transfer plate 2 that forms with interior steel plate for ± 1% with respect to design load, thereby the temperature by the control thermal medium makes the measured value of peak temperature of catalyst layer be the setting value of this peak temperature, can keep the manufacturing of reaction product thus under large-duty condition.
In addition, in above-mentioned plate-type reactor, owing to have a dividing plate 7, thereby from heat transfer plate 2 is considered it is resultful according to the aspect that the design load of the distance between the surface of heat transfer plate 2 is configured.Further, in above-mentioned plate-type reactor, owing to have dividing plate 7, thereby in the gap of 2 of heat transfer plates, form 2 with upper curtate, can be the unit catalyst filling with the section, thereby consider it is resultful from the aspect that catalyst evenly is filled into above-mentioned gap.
In addition, in above-mentioned plate-type reactor, owing to have temperature measuring apparatus 9, thereby can measure the temperature of catalyst layer 36, control the aspect of the manufacturing of carrying out product expeditiously from the temperature of carrying out thermal medium based on peak temperature and consider it is resultful according to catalyst layer 36.
In addition, in above-mentioned plate-type reactor, owing to have the thermal medium mixing arrangement, thereby consider it is resultful from the temperature aspect of controlling the thermal medium the thermal medium feedway 5 rapidly and critically.
In addition, in above-mentioned plate-type reactor, owing to have breather plug 8, thereby can only extract the catalyst of any section out, be resultful from the aspect of the high efficiency of the homogenising of catalyst layer 36 and maintenance inspection operation.
In addition, in above-mentioned plate-type reactor, owing to have gas dispenser 6 and gateway 19, further owing to keep rod 4 to be configured in and dividing plate 7 position overlapped, thereby can utilize in catalyst filling operation or the maintenance inspection operation scaffold or as the maintenance rod 4 of its holding components, from expeditiously plate-type reactor inside carry out operation aspect consider it is resultful.
Need to prove, in first plate-type reactor, also comprise form as disclosed in the patent documentation 2, shown in Figure 12, in this form in formed three conversion zones 40,41,42 along the flow direction of unstrpped gas the width of catalyst layer 43 enlarge one by one.
Plate-type reactor is difficult to precision usually to be made well, and for example for the heat-exchangers of the plate type with same formation, usually the distance between the surface of heat transfer plate has error more than 3～5mm with respect to design load.In first plate-type reactor, can be provided in the plate-type reactor that can control configuration heat transfer plate in the error range of reaction by the temperature of thermal medium, can significantly enlarge the possibility of plate-type reactor in industrial utilization.
First plate-type reactor can be used for the reaction that in the presence of solid-phase catalyst phase feed reacted, particularly the temperature in the reactor in use and being used to prepare or the normal temperature of the operation checked between the very big condition of difference under given play to more significant effect under the situation about using, and can give play to more significant effect in the following cases: in unstrpped gas and generate under the condition of gas long term exposure when using, cause these gas properties to change, thereby can produce the damage of reactor, when under such condition, using; Be accompanied by the reaction of unstrpped gas composition, reaction heat enlarges markedly, because heat makes catalyst be easy to take place deterioration, under the very important situation of the temperature treatment of catalyst layer.
＜the second plate-type reactor 〉
Second plate-type reactor has: be used to reaction vessel that reaction raw materials is reacted; Have heat-transfer pipe, be arranged side by side 2 above heat transfer plates in above-mentioned reaction vessel; Supply with the thermal medium body feeding of thermal medium body to above-mentioned heat-transfer pipe; And the gap between the heat transfer plate of adjacency is divided into 2 dividing plates with upper curtate that hold the catalyst of being filled along the ventilation direction in the reaction vessel.
Be formed with 2 above heat transfer plates and the catalyst layer more than 2 in the above-mentioned reaction vessel, these 2 above heat transfer plates in reaction vessel the ventilation direction arranged side by side, this catalyst layer more than 2 be catalyst is filled in the gap between adjacent heat transfer and form and in reaction vessel the ventilation direction arranged side by side.In reaction vessel, for example use the circular housing that is shaped as with respect to the shell that is shaped as rectangle of cross section of ventilation direction or above-mentioned cross section.
The container that above-mentioned reaction vessel is discharged from by the gap between adjacent heat transfer for the reaction raw materials of being supplied with has a pair of blow vent usually.Above-mentioned a pair of blow vent is on the one hand for being supplied to the supply port of reaction raw materials of reaction vessel, is the outlet of the reaction product that generates in the reaction vessel on the other hand.For the form of blow vent, as long as just be not particularly limited to the supply of reaction vessel and reaction product shape by the discharge of reaction vessel for carrying out reaction raw materials.A pair of blow vent is preferably relatively to setting.As such blow vent, for example can enumerate, be located at a pair of blow vent at two ends of shell or housing and following a pair of blow vent, this a pair of blow vent forms cylindric respectively in the interior perimembranous of the central part that comprises central shaft of housing and housing, and makes the reacting fluid ventilation at the cross section of housing with radial.
Above-mentioned heat transfer plate comprises 2 above heat-transfer pipes that link a direction with the periphery of cross sectional shape or ora terminalis and forms tabular.
Disclosed as patent documentation 1, the flange that such heat transfer plate can be formed at two ripple plate patterned sides ends by two ripple plates utilization that will form patterns such as circular arc, elliptic arc, rectangle continuously is bonded with each other and forms.Perhaps heat transfer plate can link the above-mentioned heat-transfer pipe more than 2 and form in periphery or ora terminalis.Perhaps heat transfer plate can be piled up formation according to the mode of joining in periphery or ora terminalis with the above-mentioned heat-transfer pipe more than 2 in reaction vessel.
The shape of heat transfer plate is determined according to the shape and the size of reaction vessel, is generally rectangle.In addition, the size of heat transfer plate is determined according to the shape and the size of reaction vessel, for example under the situation that is the rectangle heat transfer plate, its vertically (being the connection height of heat-transfer pipe) be 0.5～5m, 1～3m more preferably, its laterally (being the length of heat-transfer pipe) be 0.05～10m, 1～10m more preferably, but in normal circumstances, lateral dimension without limits.
In the reaction vessel adjacent heat transfer can according to the surperficial flange of heat transfer plate toward each other to mode arrange, also can be relative according to the recessed edge on the flange on side's heat transfer plate surface and the opposing party's heat transfer plate surface to mode arrange.Distance between adjacent heat transfer can be set in 15～50mm, the scope of 23～50mm (in the adjacent heat transfer 1.1～5 times of the half value sum of heat-transfer pipe width, more preferably 1.1～2 times) more preferably in the mean value of distance between the major axis of the heat-transfer pipe in each heat transfer plate, so that form 3～40mm, the gap of the width of 3～15mm more preferably in the transverse direction of heat-transfer pipe between heat transfer plate.Consider that from the aspect that obtains high reactivity and high reaction achievement the distance between heat transfer plate is preferably 10～50mm, more preferably 10～40mm, 20～35mm more preferably in the mean value of the distance of the major axis pipe of heat-transfer pipe.
Consider that from the aspect of carrying out the control of raw material reaction by the temperature of thermal medium body the adjustment heat-transfer pipe heat-transfer pipe in the heat transfer plate does not preferably form along the direction parallel with the ventilation direction in the reaction vessel and prolongs; Consider from the aspect of the control of carrying out raw material reaction by the temperature of adjusting thermal medium body the heat-transfer pipe, the heat-transfer pipe in the heat transfer plate more preferably form along with reaction vessel in the direction of the ventilation direction quadrature thermal medium body that prolongs, also promptly in heat-transfer pipe, flow direction for reaction vessel in the direction of ventilation direction quadrature.
Above-mentioned heat-transfer pipe by have in heat-transfer pipe the thermal medium body and and the external catalyst layer of heat-transfer pipe between the conductivity of heat of heat exchange takes place material form.As such material, can enumerate for example stainless steel and carbon steel.The cross sectional shape of heat-transfer pipe can be circle, can intend circle for ellipse or elliposoidal etc., also can be rectangle.The periphery of the cross sectional shape of so-called heat-transfer pipe is meant circular periphery, and the ora terminalis of the cross sectional shape of so-called heat-transfer pipe is meant ora terminalis or the rectangle edge on one side of intending circular longitudinal end.
2 above heat-transfer pipes cross sectional shape separately in heat transfer plate and size can also can be different for certain value.For the size of the cross sectional shape of heat-transfer pipe, for example the width of heat-transfer pipe is 3～50mm, more preferably 3～20mm or 5～50mm, and the height of heat-transfer pipe is 10～100mm, more preferably 10～50mm or 20～100mm.
Width for heat-transfer pipe, under the little situation of the heat of time per unit of giving and accepting or per unit area through heat transfer plate, from the thickness that thickens catalyst layer, the big value of getting catalyst layer thickness increase catalyst, the aspect that improves reaction speed considers, 3～20mm more preferably; Under the big situation of the heat of time per unit of giving and accepting or per unit area through heat transfer plate, from the thickness that reduces catalyst layer make conduct heat good, reduce catalytic amount and consider, 5～50mm more preferably with the aspect that reduces reaction speed.In addition, height for heat-transfer pipe, under the little situation of the heat of time per unit of giving and accepting through heat transfer plate or per unit area, the aspect that the big value of getting catalyst layer thickness from the thickness that thickens catalyst layer increases catalyst, improve reaction speed considers, more preferably 10～50mm; Under the big situation of the heat of time per unit of giving and accepting or per unit area through heat transfer plate, from the thickness that reduces catalyst layer make conduct heat good, reduce catalytic amount and consider, 20～100mm more preferably with the aspect that reduces reaction speed.
Above-mentioned thermal medium body feeding can be supplied with the device of thermal medium body for upwards stating heat-transfer pipe.As such thermal medium body feeding, for example can enumerate, the thermal medium body is supplied to whole device of 2 above heat-transfer pipes with a direction; And the thermal medium body is supplied to the part of 2 above heat-transfer pipes with a direction and the thermal medium body is supplied in the opposite direction the device of the other parts of 2 above heat-transfer pipes.The thermal medium body feeding is preferably the device that the thermal medium body is circulated by above-mentioned heat-transfer pipe inside and outside reaction tube.Consider that from aspect that the reaction the reaction vessel is controlled preferred above-mentioned thermal medium body feeding has the device of the temperature that is used to adjust the thermal medium body.
The gap of aforementioned barriers between adjacent heat transfer is provided with along the ventilation direction in the reaction vessel, forms 2 with upper curtate in above-mentioned gap.For aforementioned barriers, when when each section is filled with catalyst, so long as can keep the parts of catalyst to get final product at each section.Aforementioned barriers preferably adopts with the same material of heat transfer plate and forms, and preferably has conductivity of heat, and preferably not have reactivity, reaction in reaction vessel for the reaction in the reaction vessel be preferably to have hear resistance under the situation of exothermic reaction.In addition, consider that from the aspect that the catalyst that is filled in each section is kept aforementioned barriers preferably has rigidity.As such dividing plate, can enumerate plate, square rod, pole, net, mineral wool and the ceramic wafer of for example stainless steel manufacturing.
The shape of aforementioned barriers can for the shape that catalyst remained on the section that forms by each dividing plate, can be for the shape of joining with heat-transfer pipe, also can be the shape of driving fit.Further,, consider, be preferably the shape of joining, more preferably with the shape of the surperficial driving fit of the outer wall of heat-transfer pipe with the surface of the outer wall of heat-transfer pipe separately from aspect that the catalyst that is filled in each section is kept for aforementioned barriers.In addition, consider that from the aspect that dividing plate is set easily the preferred front view of aforementioned barriers is the tetragonal shape that is the width with the beeline between adjacent heat transfer.
For aforementioned barriers, from can be accurately and easily consider, be that the interval of 1～100L is provided with preferably according to the volume of the section that forms by dividing plate to the aspect that a section carries out the filling of catalyst.The section volume separately that is formed by dividing plate can be the same or different, from accurately and easily the aspect to whole section catalyst fillings is preferably identical.The volume of an above-mentioned section more preferably 1.5～30L, more preferably 2～15L, further be preferably 3～15L, 5～10L more preferably again.In addition, from same aspect, the distance between preferred separator (interval of dividing plate) is 0.1～1m.In addition, dividing plate be spaced apart above-mentioned heat-transfer pipe axially on the length of above-mentioned section, and be the distance that forms between the adjacent dividing plate of above-mentioned section, or form the internal face of reaction vessel above-mentioned section, that heat-transfer pipe is connecting and the distance between the dividing plate.
Aforementioned barriers can suitably be arranged on the gap between heat transfer plate according to the proterties of dividing plate.The dividing plate of shape that for example has flexual dividing plate or have a width of the beeline between heat transfer plate can be located at gap between heat transfer plate by being inserted into gap between the adjacent heat transfer in 2 above heat transfer plates that set in advance in reaction vessel.In addition, for the dividing plate of driving fit, when being arranged on heat transfer plate in the reaction vessel, can be by being arranged alternately heat transfer plate and dividing plate it be located at the gap between heat transfer plate in the shape on heat transfer plate surface.
The catalyst that is filled into above-mentioned section can use the common granular catalyst in the gap that is filled between pipe or heat transfer plate in gas-phase reaction.Catalyst can for a kind of also can be for two or more.As such catalyst, catalyst and the particle diameter (major diameter) that can enumerate particle diameter (major diameter) for example and be 1～20mm are that 3～20mm, proportion are 0.7～1.5 catalyst.In addition,, known shape be can use, spherical, cylindric, Raschig ring shape, saddle for example can be enumerated as the shape of catalyst.For the shape of catalyst, form not driving fit under the situation of the shape on the surface of heat transfer plate in aforementioned barriers, consider by the aspect that above-mentioned section leaks that from preventing catalyst the minor axis that is preferably catalyst is greater than the shape between the gap of heat transfer plate and dividing plate; Form not driving fit under the situation of the shape on the surface of heat transfer plate in aforementioned barriers, more preferably have the shape of peaked 1.2～2 times path in the gap between dividing plate and the heat transfer plate.
The filling in the gap of catalyst between adjacent heat transfer is by carrying out to each section catalyst filling.In each section, can be by being filled into the filling of carrying out catalyst in the section continuously or discontinuously with the catalyst of the capacity equal quantities of a section.The suitable occupied state of catalyst for example can be by the catalyst (catalyst layer) of being filled between section the contrast of position of upper surface (terrace) or each section in relatively the judging of calculated value of above-mentioned upper surface of the measured value of above-mentioned upper surface and each section.
In second plate-type reactor, also can further have other constitutive requirements except that above-mentioned constitutive requirements.As other such constitutive requirements, for example can enumerate: reveal preventing parts (for example breather plug), these parts have aeration, are located at the end of heat transfer plate in the downstream of the ventilation direction in the above-mentioned reaction vessel, and are used to prevent the catalyst of the filling leakage from reaction vessel; And latch for printed circuit (the dividing plate fastener that is used for fixing aforementioned barriers), these parts are located at an end of aforementioned barriers, and are used for preventing that with above-mentioned leakage parts or heat transfer plate from fastening.
Above-mentioned breather plug is aeration and the retentivity of catalyst and the parts of depositing that make each section, and it is the parts of end of the ventilation direction that can be fixed on each section with freely loading and unloading.As long as breather plug can prevent catalyst and be spilt by each section, can be located at the end of the upstream side of the ventilation direction in each section, also can be located at the end in downstream, can also be located at both ends.In addition, breather plug can all have aeration, also can be only the ventilation direction of each section be had aeration.Need to prove, passing through of the so-called gas that typically refers to one of state as reaction raw materials or reaction product, in this manual, state at reaction raw materials or reaction product is under the situation of gas fluid (for example liquid) in addition, and so-called ventilation also is meant passing through of this fluid.
Consider that from the aspect of the aeration of guaranteeing each section preferred above-mentioned breather plug is more than 10% to the aperture opening ratio of the ventilation direction of each section.The aspect that the pressure loss takes place when preventing that further breather plug is fixed on section end considers, above-mentioned aperture opening ratio more preferably more than 20%, more preferably more than 30%.
In addition,, consider from the aspect that catalyst is remained on each section for above-mentioned breather plug, preferably to the aperture of the ventilation direction of each section be below the 5mm, more preferably below the 3mm, more preferably below the 1mm.
Above-mentioned breather plug can be made of the more than one parts with aeration.As above-mentioned breather plug, for example can enumerate vent boards such as tabular net or porous plate; This vent board is configured as the air funnel of the shape of tubular; Has above-mentioned vent board and at the parts in part or all skirt section that vertically is provided with respect to vent board of its periphery; And to have cross sectional shape be first air funnel of circle or rectangle and be contained in the inboard of first air funnel and the aeration sleeve pipe of second air funnel that can be free to slide.Keep the aspect of the full intensity of catalyst to consider preferred above-mentioned air funnel, parts and aeration sleeve pipe from obtaining to be used to skirt section.Consider further preferred above-mentioned parts with skirt section from the aspect of the loading and unloading of carrying out each section end easily.
In above-mentioned parts with skirt section, consider that by the aspect that each section spills preferred above-mentioned vent board is the shape identical with the cross sectional shape of each section from preventing catalyst.For above-mentioned skirt section, consider from the fixing aspect that can freely load and unload that is easy to carry out breather plug, preferably the part of vent board periphery as for example with each section in relative to dividing plate or a pair of skirt section that joins of heat transfer plate above-mentioned skirt section is set; Consider from the aspect of the intensity that improves breather plug, preferably be located at periphery whole of vent board.In addition, the skirt section can be according to being provided with to the side-prominent mode in the two sides of vent board, also can be according to only being provided with to the side-prominent mode of the single face of vent board.
Above-mentioned breather plug can be fixed in the end of each section with freely loading and unloading.From being easy to carry out fixing and the aspect of dismounting and the aspect consideration that fixes breather plug with the intensity of enough maintenance catalyst of breather plug, be used for preferred first fastener of formation and second fastener that can fix, this first fastener is located at the section side, is heat transfer plate and/or dividing plate with freely loading and unloading; This second fastener can freely only block with this first fastener with loading and unloading, and is located at breather plug.As first and second fasteners, can enumerate the pawl of for example this hole approach axis reinforcing of Kong Yuxiang and hole, screw bolt and nut, or the like.Consider that than the aspect of the burn-back under the condition with higher preferred first and second fasteners are above-mentioned hole and the so simple and easy formation of pawl from the temperature that prevents reaction vessel.
Above-mentioned breather plug is formed by the material that the maintenance for catalyst has abundant rigidity.As such material, can enumerate for example metal and pottery such as stainless steel.From hear resistance and anti-reactive aspect, the optimizing breathing bolt adopts with the heat transfer plate identical materials and forms.
In addition, being filled in the catalyst of each section can be by taking out catalyst by the end of section behind the dismounting breather plug and extracting out with section unit.
Use accompanying drawing to be described more specifically plate-type reactor of the present invention below.
＜the second embodiment 〉
Shown in Figure 13～15, second plate-type reactor has: the shell 44 of rectangle; Have heat-transfer pipe 1 and in shell 44 relatively to 2 that are arranged side by side above heat transfer plates 2; The thermal medium body accommodation section 45 that holds the thermal medium body that is supplied to heat-transfer pipe 1; The gap of 2 of adjacent heat transfer is divided into along the ventilation directions in the shell 44 fills and keep 2 of catalyst with upper curtate 2 with upper spacer 7; Be located at the perforated plate 10,46 of the upper and lower of heat transfer plate 2; The pump 15 that is used to make the thermal medium body of thermal medium body accommodation section 45 to circulate; And be used for temperature adjustment device 47 that the temperature of thermal medium body of circulation is adjusted.
For shell 44, it forms cross sectional shape is the vent passage of rectangle, is equivalent to above-mentioned reaction vessel.In the shell 44, have in the top and bottom of shell 44 relatively to a pair of blow vent 48,48 '.Heat-transfer pipe 1 is that for example major diameter is that 30～50mm, minor axis are that the cross sectional shape of 10～20mm is oval-shaped pipe.
Heat transfer plate 2 has the shape that 2 above heat-transfer pipes 1 link with the ora terminalis of cross sectional shape.Heat transfer plate 2 forms by two ripple plates that elliptic arc is formed continuously are bonded with each other in the flange of the arc end that is formed on two ripple plates.Adjacent heat transfer 2 can according to the flange on surface toward each other to mode carry out side by side, but in the plate-type reactor of Figure 13, adjacent heat transfer 2 according to the recessed edge on the flange on the surface of a side heat transfer plate 2 and the surface of the opposing party's heat transfer plate 2 relative to mode carry out side by side.
As shown in figure 16, heat transfer plate 2 on top, middle part and bottom comprise three kinds of heat-transfer pipe a～c that sectional dimension is different respectively.Heat transfer plate 2 places the mode on the straight line to form according to the major axis with heat-transfer pipe a～c.In addition, for example the heat-transfer pipe a heat transfer plate 2, the heat-transfer pipe b that form 20% the part that accounts for height of heat transfer plate 2 heat transfer plate 2, the heat-transfer pipe c that form 30% the part that accounts for height of heat transfer plate 2 forms the heat transfer plate 2 of 40% the part that accounts for height of heat transfer plate 2.10% the part that accounts for height of heat transfer plate 2 forms with the upper end of heat transfer plate 2 and the joint board of bottom.
The cross sectional shape of heat-transfer pipe a that is formed at the top of heat transfer plate 2 is that major diameter is that 50mm, minor axis are the ellipse of 20mm, the cross sectional shape of heat-transfer pipe b that is formed at the middle part of heat transfer plate 2 is that major diameter is that 40mm, minor axis are the ellipse of 16mm, and the cross sectional shape of heat-transfer pipe c that is formed at the bottom of heat transfer plate 2 is that major diameter is that 30mm, minor axis are the ellipse of 10mm.
Need to prove, heat transfer plate 2 can be with different spacing parallel arrangings in reaction vessel integral body, but in the plate-type reactor of Figure 13, heat transfer plate 2 with same intervals (for example the beeline between the outer wall of heat-transfer pipe a is 14mm (distance is 30mm between the major axis of the heat-transfer pipe of each heat transfer plate 2)) side by side.
Thermal medium body accommodation section 45 be located at shell 44 relatively to the container of a pair of wall, be used for being formed at above-mentioned wall to the supply port that each heat-transfer pipe 1 is supplied with the thermal medium body, for example in reaction vessel integral body, according to the thermal medium body via heat-transfer pipe 1 in the mode that 45 complications in thermal medium body accommodation section flow, be divided into thermal medium body accommodation section 45 a plurality of in short transverse.
Dividing plate 7 ventilation direction in the shell 44 between adjacent heat transfer 2 is provided with.Dividing plate 7 can be provided with different interval in reaction vessel integral body, but in the plate-type reactor of Figure 13, dividing plate 7 with same intervals (for example 1,000mm) form the section of 23L volume side by side.Being provided with of dividing plate 7 is preferably at interval 5cm～2m, 10cm～1m more preferably.From carrying out to the filling of the filler in gap with section unit and carry out the aspect that accurate and easy catalyst fills and consider, the volume of the section between heat transfer plate and dividing plate is preferably 1～100L, 1.5～30L more preferably.
For dividing plate 7, when each section was filled with catalyst, use can remain on the catalyst of filling the parts of each section.Shown in Figure 17～19, dividing plate 7 can use plate or the net that has with the shape of the lateral margin of the concavo-convex driving fit on the surface of heat transfer plate 2.
In addition, for dividing plate 7, as long as the catalyst that is filled into each section not can by and dividing plate 7 between the gap drain to adjacent section, can use heat-transfer pipe a with adjacent heat transfer 2 join, not with other heat-transfer pipe b and the flange of c and the parts that recessed edge connects of heat transfer plate 2, shown in Figure 20 and 21, can use the diameter of beeline or the pole or the square rod of width with 2 of adjacent heat transfer.
Further, as shown in figure 18, dividing plate 7 can be for having the net of the mesh littler than the size of the catalyst particle of being filled, can not drain to adjacent section as long as be filled into the catalyst of each section, also can be as shown in figure 19 for having the net of mesh greater than the catalyst particle size (for example catalyst below 0.8 times of minor axis).
Two adjacent heat transfer plates 2 according to the recessed edge of the flange of side's heat transfer plate 2 and the opposing party's heat transfer plate 2 relative to mode carry out under the situation arranged side by side, as shown in figure 22, dividing plate 7 lateral margin that can use dividing plate 7 sawtooth template or net outstanding to the recessed edge of heat transfer plate 2, that separate from the flange of heat transfer plate 2.For such dividing plate 7, when according to a side flange and the opposing party's recessed edge relative to the distance (in each heat transfer plate 2 between the major axis of heat-transfer pipe 1 mean value of distance) of mode two heat transfer plates 2 arranged side by side when being 0.9～1.5 times of half value sum of the maximum minor axis of heat-transfer pipe in each heat transfer plate 2, can compatibly use such dividing plate 7.
As Figure 17～19 and shown in Figure 22, when heat transfer plate 2 is located at shell 44,, will have thus and the dividing plate 7 of the shape of the concavo-convex lateral margin that joins on the surface of heat transfer plate 2 is located between two heat transfer plates 2 by the dividing plate 7 that is arranged alternately heat transfer plate 2 and connects with it.As Figure 20 and shown in Figure 21, have the diameter of beeline of 2 of adjacent heat transfer or width dividing plate 7 can by be arranged alternately heat transfer plate 2 and and its dividing plate that connects 7 be located between two heat transfer plates 2, also can be provided with between the adjacent heat transfer 2 by the heat transfer plate 2 that has been inserted into and established.Net or sheet metal are such has flexual dividing plate 7 and also can be provided with between the adjacent heat transfer 2 by the heat transfer plate 2 that has been inserted into and established.
Perforated plate 10,46 is respectively with 20～99% aperture opening ratio the plate in 0.20～0.99 times hole that diameter is the major diameter of the catalyst of being filled to be set.In the plate-type reactor of Figure 13, in order to prevent the ventilation in the gap between the wall that is disposed at outermost heat transfer plate 2 and shell 44, as shown in figure 15, form perforated plate 10,46 by the ora terminalis that is disposed at outermost heat transfer plate 2 to the mode in the gap of the wall of shell 44 according to obturation.
Pump 15 uses the device of the thermal medium body that can carry desired temperature.In addition, in temperature adjustment device 47, use can be controlled at the temperature of thermal medium body the devices such as heat exchanger of desired temperature.Thermal medium body accommodation section 45, pump 15 and temperature adjustment device 47 constitute the thermal medium body feeding.
Catalyst to the filling of 2 of heat transfer plates by carrying out to each section catalyst filling.Because the section that formed by heat transfer plate 2 and dividing plate 7 all has identical volume, thereby fill and the catalyst of the equal capacity of capacity of a section (for example be 95～100% volume) with respect to a section capacity to each section.
The comparison of the theoretical value of height that the good occupied state of catalyst can be when filling the catalyst of scheduled volume and the comparison (for example measured value is in 10% with respect to the error of theoretical value) of measured value or the packed height by the catalyst between each section (for example the difference of the packed height between each section be packed height 2% in) judge.
In addition, dividing plate 7 have the hole that hangs over perforated plate 46 or be located at heat transfer plate 2 the end the hole or take turns hook on such holding section, by only coming tensioning that (Zhang Let is set this dogging in the holding section) dividing plate 7, also it can be located at the gap of 2 of adjacent heat transfer thus.If utilize such formation, the material that then mineral wool etc. can not had conformality is used for dividing plate 7.
Above-mentioned plate-type reactor is owing to have a dividing plate 7, thereby by with section unit's catalyst filling under constant state, can be on reactor monolith even catalyst filling.Therefore, compare the filling that to carry out more easily that catalytic amount is accurate with respect to design load, the occupied state (for example packed density, voidage) between each section can be homogeneous with filling to the catalyst of 2 of the heat transfer plates that does not form such section.
In addition, for above-mentioned plate-type reactor, because whole sections of being formed by heat transfer plate 2 and dividing plate 7 have same capability, thereby used catalyst is certain in catalyst filling operation.Therefore, compare, can more promptly carry out the filling operation of catalyst with catalyst filling to 2 of the heat transfer plates that does not form such section.
Further, because above-mentioned plate-type reactor has dividing plate 7, thereby can judge the occupied state of catalyst with section unit.Therefore, under the occupied state condition of poor of catalyst, by once more only to being judged as bad section catalyst filling, thereby can revise the occupied state of catalyst.Therefore, compare, can more easily carry out the adjustment of catalyst filling operation with catalyst filling to 2 of the heat transfer plates that does not form such section.
＜the three embodiment 〉
Shown in Figure 23～25, in second plate-type reactor, for example, replace perforated plate 46 and have 2 above breather plugs 8 of the bottom that is aeration and inaccessible each section, in addition, have the formation same with the plate-type reactor of above-mentioned second form.
In the present embodiment, it is the vent passage of rectangle that shell 44 forms cross sectional shape, is equivalent to above-mentioned reaction vessel.Shell 44 have in the top and bottom of shell 44 relatively to a pair of blow vent 48,48 ', and constitute by the outer casing end 49 that contains blow vent 48, the housing main body that contains the outer casing end 49 ' of blow vent 48 ' and hold heat transfer plate 2.Outer casing end 49,49 ' can freely connect with respect to housing main body separately with loading and unloading.Heat-transfer pipe 1 is that for example major diameter is that 20～100mm, minor axis are that the cross sectional shape of 5～50mm is oval-shaped pipe.
Heat transfer plate 2 has the shape that 2 above heat-transfer pipes 1 link with the ora terminalis of cross sectional shape.Heat transfer plate 2 is bonded with each other in the flange of the arc end that is formed on two ripple plates by two ripple plates that elliptic arc is formed continuously and forms.Adjacent heat transfer 2 can according to surperficial flange toward each other to mode arranged side by side, but in the plate-type reactor of Figure 23, according to the recessed edge on the flange on the surface of side's heat transfer plate 2 and the surface of the opposing party's heat transfer plate 2 relative to mode arranged side by side.
For example, as shown in figure 16, heat transfer plate 2 on top, middle part and bottom comprise three kinds of heat-transfer pipe a～c that sectional dimension is different respectively.Heat transfer plate 2 forms according to the major axis configuration mode in a straight line of heat-transfer pipe a～c.In addition, in the present embodiment, for example the heat-transfer pipe a heat transfer plate 2, the heat-transfer pipe b that form 30% the part that accounts for height of heat transfer plate 2 heat transfer plate 2, the heat-transfer pipe c that form 25% the part that accounts for height of heat transfer plate 2 forms the heat transfer plate 2 of 45% the part that accounts for height of heat transfer plate 2.
The cross sectional shape of heat-transfer pipe a that is formed at the top of heat transfer plate 2 is that major diameter is that 50mm, minor axis are the ellipse of 20mm, the cross sectional shape of heat-transfer pipe b that is formed at the middle part of heat transfer plate 2 is that major diameter is that 40mm, minor axis are the ellipse of 16mm, and the cross sectional shape of heat-transfer pipe c that is formed at the bottom of heat transfer plate 2 is that major diameter is that 30mm, minor axis are the ellipse of 10mm.
Need to prove, in the present embodiment, heat transfer plate 2 can be with different spacing parallel arrangings in reaction vessel integral body, but in the plate-type reactor of Figure 23, heat transfer plate 2 with same intervals (for example the beeline between the outer wall of heat-transfer pipe a is 5mm (distance is 25mm between the major axis of the heat-transfer pipe of each heat transfer plate 2)) side by side.
Thermal medium body accommodation section 45 is identical with the thermal medium body accommodation section 45 in above-mentioned second mode.
Dividing plate 7 ventilation direction in the shell 44 between adjacent heat transfer 2 is provided with.Dividing plate 7 can be provided with different intervals in reaction vessel integral body, but in the plate-type reactor of Figure 23, arranged side by side with same intervals (for example 500mm), the section of formation 25L volume.In the present embodiment, as shown in figure 26, dividing plate 7 for example for having the stainless steel making sheet with the shape of the lateral margin of the concavo-convex driving fit on the surface of heat transfer plate 2, has window 20 in the bottom.
As shown in figure 27, breather plug 8 is located at the bottom of each section.Breather plug 8 has the vent board 21 of the identical rectangle of the cross sectional shape of each section, for example as shown in figure 28 by hang down first skirt section 22 of establishing and by vertical second skirt section 23 of establishing, the long limit of vent board 21 of the minor face of vent board 21 downwards downwards.In first skirt section 22, as shown in figure 28, the card that forms rectangle ends window 24 and and is located at the card claw stop 50 on its next door.
As shown in figure 29, breather plug 8 is with vent board 21 and each skirt section 22 and 23 shapes of launching, will be in the skirt section 22 form that card ends window 24 and as the border bending of stainless steel making sheet between vent board 21 and each skirt section 22,23 of the grooving of card claw stop 50, and, formed breather plug 8 thus by edge welding with each skirt section.Vent board 21 for example is the plate with the hole of the circle of aperture opening ratio 30% formation 2mm.
In first skirt section 22, card claw stop 50 bends projection laterally with two the parallel groovings from the following ora terminalis in first skirt section 22 and forms.In each first skirt section 22, card ends window 24 and card claw stop 50 and concerns the identical setting of respectively doing for oneself with respect to the position of vent board 21.Therefore, relatively in to a pair of first skirt section 22, a side card end window 24 and the opposing party's card claw stop 50 relative to a, side card claw stop 50 and the opposing party's card end window 24 relative to.In addition, card ends window 24 and forms according to having the width that holds card claw stop 50 and the size of height, and the window 20 of dividing plate 7 comprises width and the size highly that card ends window 24 and card claw stop 50 simultaneously and forms according to having.
Breather plug 8 upwards inserts in each section vent board 21 from the lower end of each section.Block laterally afterburning of claw stop 50 opposing this moment and press to dividing plate 7, when arriving window 20, as shown in figure 30, discharge and enter window 20, be limited to window 20 from the extruding of dividing plate 7.Window 20 is equivalent to first fastener, and card claw stop 50 is equivalent to second fastener.
In the present embodiment, perforated plate 10 is for being provided with the plate in 0.3～0.8 times hole that diameter is the major diameter of the catalyst of being filled with 20～40% aperture opening ratio.In the plate-type reactor of Figure 23, for perforated plate 10, in order to prevent the ventilation in the gap between the wall that is disposed at outermost heat transfer plate 2 and shell 44, as shown in figure 25, form perforated plate 10 according to the mode of obturation from the ora terminalis that is disposed at outermost heat transfer plate 2 to the gap of the wall of shell 44.
Pump 15 and temperature adjustment device 47 are identical with temperature adjustment device 47 with pump 15 in above-mentioned first mode.Thermal medium body accommodation section 45, pump 15 and temperature adjustment device 47 constitute the thermal medium body feeding.
Catalyst to the filling of 2 of heat transfer plates by carrying out to each section catalyst filling.Because heat transfer plate 2 and dividing plate 7 formed sections all have same volume, thereby in the present embodiment, for example, fill the catalyst of the capacity that equates with the capacity of a section (for example be 97～103% volume) to each section with respect to the capacity of a section.
In the present embodiment, the comparison of the packed height of the comparison (for example measured value is in 3% with respect to the error of theoretical value) of the theoretical value of the packed height that the good occupied state of catalyst can be by catalyst and measured value or the catalyst between each section (for example the difference of the packed height between each section be packed height 5% in) judge.
Under the occupied state condition of poor of the catalyst of one section, extract the breather plug 8 of this section, only extract the catalyst that is filled into this section out from the lower end of this section.For the window 20 of dividing plate 7, because it forms according to comprise the size that card ends window 24 and card claw stop 50 fixedly the time at breather plug 8, thereby window 20 ends window 24 and blocks claw stop 50 and carry out opening with respect to the card of two adjacent breather plugs 8 across dividing plate 7.Further, because card ends window 24 and forms with the size that comprises card claw stop 50, thereby the card of the side in adjacent two breather plugs 8 of dividing plate 7 ends card claw stop 50 openings of window 24 with respect to the opposing party, and the opposing party's card ends card claw stop 50 openings of window 24 with respect to a side.Thus, the card claw stop 50 that card ends is not blocked by adjacent breather plug 8 with respect to the space of the downside of vent board 21, thereby in the lower side space of vent board 21, can directly push card claw stop 50.Thereby for breather plug 8, for example as shown in figure 31, use front end to have and to be inserted into the instrument that card ends the hook in the window 24, end the window 20 of window 24 and dividing plate 7 by card across the adjacent breather plug 8 of dividing plate 7, utilize above-mentioned hook to push card claw stop 50, can end by the card between releasing card claw stop 50 and the window 20 and it be unloaded.
After catalyst taken out, once more breather plug 8 is inserted from the lower end of this section and fixing, and, can carry out the filling of catalyst in each section again thus to this section catalyst filling.
Above-mentioned plate-type reactor is owing to have a dividing plate 7, thereby by with section unit's catalyst filling under constant state, can on reactor monolith catalyst evenly be filled.Therefore, compare, can more easily carry out the accurate filling of catalyst with catalyst filling to 2 of the heat transfer plates that does not form such section.
In addition, in above-mentioned plate-type reactor, because the whole sections that form by heat transfer plate 2 and dividing plate 7 have same capability, thereby used catalyst is certain in catalyst filling operation.Therefore, compare, can more promptly carry out the filling operation of catalyst with catalyst filling to 2 of the heat transfer plates that does not form such section.
Further, because above-mentioned plate-type reactor has dividing plate 7, thereby can judge the occupied state of catalyst with section unit.Therefore, under the occupied state condition of poor of catalyst, only to being judged as bad section catalyst filling, can revise the occupied state of catalyst by once more.Therefore, compare, can more easily carry out the adjustment of catalyst filling operation with catalyst filling to 2 of the heat transfer plates that does not form such section.
In addition, in above-mentioned plate-type reactor,, therefore can easily carry out the extraction of catalyst with section unit owing to have breather plug 8.Therefore, under the occupied state condition of poor of catalyst, unload the breather plug that is judged as bad section, catalyst is extracted out by section,, can easily revise the occupied state of the catalyst of particular section thus again to this section catalyst filling.Therefore, compare, can further easily carry out the adjustment of the filling operation of catalyst with catalyst filling to 2 of the heat transfer plates that does not form such section.
In addition, because breather plug 8 has the vent board 21 and first and second skirt sections 22,23 of rectangle, thereby consider it is excellent from the aspect of the abundant intensity of the catalyst layer of supported each section.In addition, obtain because breather plug 8 is die-cut, bending and welding by steel plate, thereby can easily obtain so excellent breather plug 8.
In addition, for breather plug 8, relatively to a pair of first skirt section 22 have card separately and end window 24 and block claw stop 50, relatively in to a pair of first skirt section 22, one side's card end window 24 and the opposing party's card claw stop 50 relative to, one side's card claw stop 50 and the opposing party's card end window 24 relative to, thereby in the adjacent breather plug 8 of dividing plate 7, under the situation of or butt not overlapping at the card claw stop 50 outstanding by each breather plug 8, with the fixing breather plug 8 of full intensity, and carry out the dismounting of breather plug 8 easily, consider it is excellent from above-mentioned viewpoint.
Further, because the window 20 of dividing plate 7 is to form to comprise the size that breather plug 8 solid timing cards end window 24 and card claw stop 50, thereby arbitrary card claw stop 50 of two breather plugs 8 that join with dividing plate 7 is and can freely load and unload only blocks.Like this, because the dividing plate 7 of the window 20 with single specification is set, thereby consider that from the viewpoint of the free construct for handling that constitutes breather plug 8 at low cost above-mentioned plate-type reactor is excellent.
In addition, in above-mentioned plate-type reactor, owing to fix breather plug 8 ending little the contacting of such contact area by card claw stop 50 with card between the window 20 below the vent board 21, thereby the card claw stop 50 when preventing to be used for the reaction under the such higher temperatures condition of oxidation reaction and the aspect consideration of the burn-back between the window 20 are excellent.
Need to prove, in above-mentioned plate-type reactor, be that the window 20 as second fastener is located at dividing plate 7, but also the second such fastener can be located at the bottom of heat transfer plate 5, also can breather plug 8 similarly be set with the plate-type reactor of Figure 23.So, for breather plug,, also can be undertaken fixedly to block with freely loading and unloading and end by the bottom that utilizes heat transfer plate 5 even without dividing plate.Further, can second fastener be set, in this case, consider it is resultful from the aspect of the constant intensity that improves breather plug in the bottom of dividing plate 7 and this two place, bottom of heat transfer plate 5.
In addition, for dividing plate, for example can or the size in the gap that is generated between place, dividing plate and the heat transfer plate be set according to the kind of second fastener, distance different between heat transfer plate are used various dividing plates.As such dividing plate, for example can enumerate: have and the net of the shape of the lateral margin of the concavo-convex driving fit mutually on the surface of heat transfer plate 2, the diameter of beeline or the plate of width with shown in Figure 19 with 2 of adjacent heat transfer as Figure 18; Or as Figure 20 and pole or square rod shown in Figure 21; Lateral margin as shown in figure 22, dividing plate 7 to the recessed edge of heat transfer plate 2 outstanding and with sawtooth template or the net separated by the flange of heat transfer plate 2; And the parts that do not have the material of conformality based on mineral wool etc.
In the present embodiment, under having the situation of mesh (for example below 0.5 times of major diameter of catalyst) of size of the degree that catalyst can not spill, can compatibly use for example used netting gear of this dividing plate as Figure 18 and dividing plate shown in Figure 19.The mesh of the net that dividing plate is used is preferably dimensioned to be the mesh below 0.8 times (order Open I) of the path of catalyst.
In addition, in the present embodiment,, can compatibly use as Figure 20 and dividing plate shown in Figure 21 not forming between heat transfer plate and the dividing plate under the situation in gap of width that catalyst spills degree.In addition, in the present embodiment, a side flange and the opposing party's recessed edge with relative to the distance (mean value of distance between the major axis of the heat-transfer pipe 1 in each heat transfer plate 2) of form two heat transfer plates 2 arranged side by side when being 0.9～1.5 times of half value sum of maximum minor axis of the heat-transfer pipe in each heat transfer plate 2, can compatibly use dividing plate as shown in figure 22.
For dividing plate,, also can use above-mentioned dividing plate arbitrarily for example not being provided with under the situation of second fastener in the dividing plate.In addition, be under the situation of window at for example second fastener, can use the plate-shaped member that the window that can support breather plug can be set.This external for example second fastener is under the situation of window, and dividing plate can use the mesh members of the mesh with sufficient size of using as above-mentioned window.
For as Figure 26,18,19 and shown in Figure 22, have the dividing plate with the shape of the concavo-convex lateral margin that joins on the surface of heat transfer plate, when heat transfer plate is located at shell, by be arranged alternately heat transfer plate and and its dividing plate that connects be located between two heat transfer plates.For Figure 20 and the diameter with the beeline between adjacent heat transfer shown in Figure 21 or the dividing plate of width, can by be arranged alternately heat transfer plate and and its dividing plate that connects and it is located between two heat transfer plates, also can be provided with between the adjacent heat transfer by the heat transfer plate that has been inserted into and established.Net or cloth or sheet metal are such has flexual dividing plate and also can be provided with between the adjacent heat transfer by the heat transfer plate that has been inserted into and established.
In addition, dividing plate have the hole that hangs over breather plug 8 or be located at heat transfer plate 2 the end the hole or take turns hook on so extra fastener, by only coming tensioning that dividing plate is set this dogging, also it can be located at the gap of 2 of adjacent heat transfer thus at fastener.Preferred such formation is considered in the aspect that is used for dividing plate from the material that mineral wool etc. is not had conformality.
In addition, for the breather plug in the above-mentioned plate-type reactor 8, shown in figure 32, also can not use card claw stop 50 and use front end to have the breather plug of the card claw stop 51 that the lower surface with window 20 joins.From breather plug being firmly fixed at the aspect of each section, further preferred such breather plug.In addition, for breather plug, when using for a long time, plate-type reactor can prevent also the aspect that breather plug falls, catalyst is come off by the gap between heat transfer plate from considering it also is effective with card claw stop 51.
In addition, for breather plug,, just can use the breather plug of various forms as long as have the so suitable free construct for handling of window 20 and card claw stop 50.As such breather plug, for example can enumerate as shown in figure 33 the cylinder that forms with net or vent board, plate as shown in figure 34 with passage, as Figure 35 and shown in Figure 36 with a pair of skirt section support the parts of the shape of vent board or net, the parts of the case shape that constitutes by net as Figure 37 and surface shown in Figure 38.
Further, for breather plug based on other form of such form, can enumerate the breather plug of sleeve structure as shown in figure 39 with first breather pipe 52 and second breather pipe 53, described first breather pipe 52 has aeration with respect to the ventilation direction of each section, described second breather pipe 53 has aeration with respect to the ventilation direction of each section, and slides at the internal freedom of first breather pipe 52.Under the situation of using such breather plug, for example dividing plate 7 be provided with extend to by the outstanding flange portion 54 in the surface of the bottom of dividing plate 7, with breather plug that dividing plate 7 with two ends joins and mounting in flange portion 54, utilize the flexible of the fixing glide direction towards breather plug of steady pin 55, thus above-mentioned breather plug is arranged at the bottom of each section.
Steady pin 55 for example by fixed axis, be located at the wheel of one end and have flexual sheet metal and constitute, described sheet metal is arranged at its other end with the direction of prolonging the outgoing direction quadrature with respect to fixed axis.If the passage of steady pin 55 below breather plug inserted, the deflection releasing of sheet metal behind sheet metal deflection the passing through passage during then by passage, steady pin 55 forms the state that hangs from above from breather plug.In addition, by the wheel of tractive steady pin 55, sheet metal by passage, is extracted steady pin 55 thus in deflection, further by second breather pipe 53 is slided, can unload above-mentioned breather plug from the below of heat transfer plate.
Perhaps, breather plug for above-mentioned other form, can enumerate the breather plug with first breather pipe 52, second breather pipe 53 and afterburning parts 56 of having as shown in figure 40, described afterburning parts 56 are to the such parts of helical spring by the outstanding direction reinforcing of first breather pipe 52 to second breather pipe 53.This breather plug also is arranged at the bottom of each section by the dividing plate 7 with flange portion 54.The reinforcing that resists afterburning parts 56 makes the breather plug withdrawal and this breather plug is positioned on the flange portion 54, thus this breather plug is arranged at the bottom of each section.In addition, make the breather plug withdrawal, can unload described breather plug by the below of heat transfer plate by the reinforcing that resists afterburning parts 56.The slip of the steady pin 55 and second breather pipe 53 can be by carrying out on the passage with the bottom of the wheel that is hooked on steady pin 55 of instrument shown in Figure 31 or second breather pipe 53.
Second manufacture method of＜reaction product 〉
Second manufacture method of reaction product of the present invention is to use above-mentioned second plate-type reactor to make the method for reaction product, and this method comprises operation from the reaction product that the operation of the thermal medium body of desired temperature, gap supply response raw material and obtain between the adjacent heat transfer that is filled with catalyst discharge from above-mentioned gap to above-mentioned heat-transfer pipe that supply with.In first method, above-mentioned reaction raw materials is an ethene; Being selected from by carbon number is at least a in the group formed of 3 and 4 the hydrocarbon and the tert-butyl alcohol or to be selected from by carbon number be at least a in the group formed of 3 and 4 unsaturated aliphatic aldehyde; Carbon number is the hydrocarbon more than 4; Dimethylbenzene and/or naphthalene; Alkene; Carbonyls; Cumene hydroperoxide; Butylene; Or ethylbenzene, above-mentioned reaction product is an ethylene oxide; Carbon number is that 3 and 4 unsaturated aliphatic aldehyde and/or carbon number are 3 and 4 unrighted acid; Maleic acid; Phthalic acid; Alkane; Alcohol; Acetone and phenol; Butadiene; Or styrene.
Second plate-type reactor is applicable to the catalytic operation of fixed bed, particularly is applicable to owing to high reaction heat the reaction process that catalyst degradation or reaction achievement can reduce can take place in such reaction process.Particularly second plate-type reactor can be applicable to the reaction raw materials of the fluid that gas or liquid etc. can circulate in being filled with the catalyst layer of catalyst, but compares with the situation of liquid condition, more can compatibly be used to be difficult under the situation of gas of heat extraction.
For example, the reaction of effectively suitable second plate-type reactor is following reaction: above-mentioned raw materials is an ethene; Being selected from by carbon number is at least a in the group formed of 3 and 4 the hydrocarbon and the tert-butyl alcohol or to be selected from by carbon number be at least a in the group formed of 3 and 4 unsaturated aliphatic aldehyde; Carbon number such as normal butane or benzene is the hydrocarbon more than 4; Dimethylbenzene and/or naphthalene; Alkene; Carbonyls; Cumene hydroperoxide; Butylene; Or ethylbenzene, resulting above-mentioned reaction product is an ethylene oxide; Carbon number is that 3 and 4 unsaturated aliphatic aldehyde and/or carbon number are 3 and 4 unrighted acid; Maleic acid; Phthalic acid; Alkane; Alcohol; Acetone and phenol; Butadiene; Or styrene.
Particularly preferably be, second plate-type reactor be applicable to known be easy to produce heat spot, the gas phase contact oxidation.Can enumerate reaction raw materials and be to be selected from and be reaction raw materials at least a in the group formed of 3 and 4 the hydrocarbon and the tert-butyl alcohol or be at least a reaction of the reaction raw materials in the group formed of 3 and 4 unsaturated aliphatic aldehyde for being selected from by carbon number by carbon number.
Specifically, be 3 hydrocarbon as above-mentioned carbon number, can enumerate propylene, propane.As above-mentioned carbon number is 4 hydrocarbon, can enumerate isobutene, butylene class, butanes.In addition, be 3 and 4 unsaturated aliphatic aldehyde as above-mentioned carbon number, can enumerate methacrylaldehyde, MAL, be 3 and 4 unrighted acid as carbon number, can enumerate acrylic acid, methacrylic acid.
In second manufacture method of reaction product, in catalyst, can utilize used well-known catalysts in the existing haptoreaction of stating reaction raw materials in the use, for example use the haptoreaction of the above-mentioned reaction raw materials of multi-tubular reactor.May be combined in inert particles such as not having reactive mullite ball in the above-mentioned haptoreaction in the catalyst.In addition, in second manufacture method of reaction product, temperature for the thermal medium body that is supplied to heat-transfer pipe, for example can be with existing haptoreaction, for example use the reaction condition in the haptoreaction of above-mentioned reaction raw materials of multi-tubular reactor to be benchmark, try to achieve by the optimization of the reaction condition in the reaction of using second plate-type reactor.Further, for other reaction condition in second manufacture method of reaction product, for example can similarly try to achieve with the temperature of above-mentioned thermal medium body by the optimization of utilizing known technology.Perhaps, for the reaction condition in second manufacture method of reaction product, can be suitable for the reaction condition of the 3rd manufacture method of first manufacture method of above-mentioned reaction product or aftermentioned reaction product.
The 3rd manufacture method of＜reaction product 〉
The 3rd manufacture method of reaction product is (A) method or (B) method: (A) supply response raw mix in possessing the plate-type reactor that is formed at the catalyst layer between the heat transfer plate, this reacting material mixture contain to be selected from by carbon number and are reaction raw materials at least a in the group formed of 3 and 4 the hydrocarbon and the tert-butyl alcohol and contain molecularity oxygen; Above-mentioned reaction raw materials is carried out catalytic gas phase oxidation, make that to be selected from by unsaturated hydrocarbons and carbon number be at least a reaction product in the group formed of 3 and 4 unsaturated aliphatic aldehyde.(B) supply response raw mix in possessing the plate-type reactor that is formed at the catalyst layer between the heat transfer plate, this reacting material mixture contain that to be selected from by carbon number be at least a and molecularity oxygen of the reaction raw materials in the group formed of 3 and 4 unsaturated aliphatic aldehyde; Above-mentioned reaction raw materials is carried out catalytic gas phase oxidation, make that to be selected from by carbon number be at least a reaction product in the group formed of 3 and 4 unrighted acid.
Further, in the 3rd manufacture method of reaction product, above-mentioned plate-type reactor is split into 2 different above conversion zones of average layer thickness of catalyst layer, supply with the thermal medium body that independently carries out the temperature adjustment to above-mentioned 2 above conversion zones, the heat that is generated by above-mentioned oxidation is carried out heat extraction across above-mentioned heat transfer plate, and the temperature in the above-mentioned catalyst layer of independent control.
Further, in the 3rd manufacture method of reaction product, the temperature T (S1) that is supplied to the above-mentioned thermal medium body of conversion zone S1 is higher than the temperature T (S2) of the above-mentioned thermal medium body that is supplied to conversion zone S2, described conversion zone S1 approaches the inlet of above-mentioned reacting material mixture most, described conversion zone S2 is adjacent with above-mentioned conversion zone S1, and is positioned at the downstream of reacting material mixture stream.
Further, in the 3rd manufacture method of reaction product, be that reaction raw materials at least a in the group formed of 3 and 4 the hydrocarbon and tert-butyl alcohol load when carrying out oxidation, above-mentioned reaction raw materials is more than 150 liter per hours [converting through standard state (0 ℃ of temperature, 101.325kPa)] with respect to per 1 liter of catalyst to above-mentioned being selected from by carbon number; To above-mentioned being selected from by carbon number is that reaction raw materials at least a in the group formed of 3 and 4 unsaturated aliphatic aldehyde load when carrying out oxidation, above-mentioned reaction raw materials is more than 160 liter per hours [converting through standard state (0 ℃ of temperature, 101.325kPa)] with respect to per 1 liter of catalyst.
Used reaction raw materials is that being selected from by carbon number is reaction raw materials at least a in the group formed of 3 and 4 the hydrocarbon and the tert-butyl alcohol or to be selected from by carbon number be reaction raw materials at least a in the group formed of 3 and 4 unsaturated aliphatic aldehyde in the 3rd manufacture method of reaction product.As above-mentioned carbon number is 3 hydrocarbon, can enumerate propylene, propane.As above-mentioned carbon number is 4 hydrocarbon, can enumerate isobutene, n-butene, isobutene, normal butane, iso-butane.As above-mentioned carbon number is 3 and 4 unsaturated aliphatic aldehyde, can enumerate methacrylaldehyde, MAL.
Just be not particularly limited as long as the state of these reaction raw materials has the flowability that circulates in above-mentioned catalyst layer, but preferred exemplary goes out the state for gas (reaction raw materials gas).
In addition, be that 3 and 4 unsaturated aliphatic aldehyde and carbon number are in 3 and 4 the unrighted acid at unsaturated hydrocarbons, carbon number as above-mentioned reaction product, as unsaturated hydrocarbons, can enumerate butadiene; As carbon number is 3 and 4 unsaturated aliphatic aldehyde, can enumerate methacrylaldehyde, MAL; As carbon number is 3 and 4 unrighted acid, can enumerate acrylic acid, methacrylic acid, maleic acid, maleic anhydride.
Think that the 3rd manufacture method of reaction product is the reasons are as follows that above-mentioned total overall reaction product can be suitable for herein.
As above-mentioned reason, for example can enumerate, by carbon number is that 3 propylene is made methacrylaldehyde, to be by carbon number that 4 isobutene is made MAL and made basic composition (for example molybdenum (Mo)-bismuth (Bi) is), method for making and the shape of the used catalyst of butadiene by n-butene basic identical, and the reaction formation in the manufacturing of this reaction product, operation are industrial identical.Further can enumerate, by making acrylic acid as the methacrylaldehyde of unsaturated aliphatic aldehyde, making methacrylic acid and make the catalyst that also uses same basic composition (for example molybdenum (Mo)-vanadium (V) is), shape in the maleic anhydride, utilize identical reaction formation, operation to carry out industrial reaction manufacturing by the butylene class by MAL.These reactions are the catalytic gas phase oxidation that utilizes molecularity oxygen, and are the reactions that is attended by big heat release, and according to the inventor's opinion, these reactions have same response characteristic, therefore think effectively the 3rd manufacture method of application response product.
The above-mentioned reacting material mixture that is supplied to above-mentioned plate-type reactor contains reaction raw materials, molecularity oxygen and contains nitrogen, steam etc. as required reaction is inert gasses.Above-mentioned reaction raw materials can be a kind formation only, and also can be the mixture (for example mist) that mixes more than 2 kinds.The composition of above-mentioned reacting material mixture (for example reaction mixture gas body) is suitably selected according to purpose.
Above-mentioned reaction raw materials is not particularly limited with respect to the content of above-mentioned reacting material mixture, as the total amount of reaction raw materials, is preferably 5～13 moles of %.In addition, above-mentioned molecularity oxygen is preferably 1～3 times of amount of reaction raw materials total amount with respect to the content of above-mentioned reacting material mixture.
Above-mentioned inert gasses is the total amount of deduction reaction raw materials from above-mentioned reacting material mixture total amount and the value of molecularity oxygen amount with respect to the content of above-mentioned reacting material mixture.In addition, above-mentioned inert gasses can be used the inert gas that the tail gas of being discharged by reaction system is recycled.
In the 3rd manufacture method of reaction product, can use known catalyst according to purpose.As the composition of catalyst, can enumerate the metal oxide that contains molybdenum, tungsten, bismuth etc. or contain the metal oxide of vanadium etc.The metal oxide powder of this composition is shaped to spherical, granular or ring-type, after at high temperature firing, as catalyst.In addition, the shape of catalyst can adopt known shape, and can suitably use diameter is the spherical of 1～15mm (millimeter); Perhaps oval equivalent diameter shape, that have 1～15mm in addition is granular; Perhaps the shape of the ring-type of cylindrical center's perforate of cylinder, the circle external diameter is that 4～10mm, circle internal diameter are 1～3mm, highly are the shape of 2～10mm.More preferably above-mentioned diameter, equivalent diameter, circle external diameter and highly be the catalyst of 3～5mm.
Reaction raw materials is under the situation of propylene, and as above-mentioned metal oxide, suitably example goes out the compound shown in 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) ... formula (1)
In the above-mentioned formula (1), Mo represents molybdenum; Bi represents bismuth; Co represents cobalt; Ni represents nickel; Fe represents iron; X represents to be selected from least a element in the group that sodium, potassium, rubidium, caesium and thallium form; Y represents to be selected from least a element in the group of being made up of boron, phosphorus, arsenic and tungsten; Z represents to be selected from least a element in the group of being made up of magnesium, calcium, zinc, cerium and samarium; Q represents halogens; Si represents silica; O represents oxygen.
In addition, in above-mentioned formula (1), a, b, c, d, e, f, g, h, i, j and k represent the atomic ratio of Mo, Bi, Co, Ni, Fe, X, Y, Z, Q, Si and O respectively, molybdenum atom (Mo) is 12 o'clock, 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, the serve as reasons value of state of oxidation decision of each element of k.
On the other hand, be under the situation of methacrylaldehyde at reaction raw materials, as above-mentioned metal oxide, suitably example goes out the compound shown in 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) ... formula (2)
In the above-mentioned formula (2), X represents to be selected from least a element in the group of being made up of Nb and W.Y represents to be selected from least a element in the group of being made up of Mg, Ca, Sr, Ba and Zn.Z represents to be selected from least a element in the group of being made up of Fe, Co, Ni, Bi, Al.Wherein Mo, V, Nb, Cu, W, Sb, Mg, Ca, Sr, Ba, Zn, Fe, Co, Ni, Bi, Al, Si, C and O are the symbol of element.
In addition, in above-mentioned formula (2), a, b, c, d, e, f, g, h and i represent each atoms of elements ratio, are 12,0＜a≤12,0≤b≤12,0≤c≤12,0≤d≤8,0≤e≤500,0≤f≤500,0≤g≤500,0≤h≤500 with respect to molybdenum atom (Mo); I is definite value by the oxidizability of each composition except that C among above-mentioned each composition.
In the reactor of practicality, require the processing load of the reaction raw materials of raising unit catalyst, to increase the productivity ratio of goal response product.But, under the situation of the processing load of the reaction raw materials that improves the unit catalyst, need be used for suitably controlling the heat that generates by reaction and prevent heat spot, prevent the damage of catalyst and improve the conversion ratio of reaction raw materials and the scheme of the yield of goal response product.
For corresponding, for the plate-type reactor of the 3rd manufacture method that is used for reaction product, its shape etc. is not particularly limited, but is feature with following (1) and (2).
(1) is divided into 2 different above conversion zones of average layer thickness of the catalyst layer that between heat transfer plate, forms.
(2) supply with the thermal medium body of adjusting through temperature to 2 above conversion zones, independently supply with the thermal medium body of adjusting through temperature with upper curtate to 2 in case of necessity, to carry out heat extraction across heat transfer plate by the heat that catalytic gas phase oxidation reaction generates, can independently control the temperature in the catalyst layer thus.
As such plate-type reactor, can utilize the plate-type reactor of the invention described above.In the 3rd manufacture method of reaction product, consider from the two the aspect of effect of the effect of the 3rd manufacture method of the effect that obtains plate-type reactor of the present invention and reaction product, preferably in second method, use plate-type reactor of the present invention.
Put down in writing the embodiment of the above-mentioned plate-type reactor of the 3rd manufacture method that is used for reaction product below.Need to prove, in the record below,, use " reacting gas " of one of the mode of reacting fluid that reaction raw materials, reacting material mixture are described sometimes and the general name of the mixture of the reaction product that generates by reaction etc. for easy.
As the 1st mode of plate-type reactor, can enumerate that catalyst filling forms conversion zone in the space of a pair of heat transfer plate clamping, have plate-type reactor from the thermal medium body stream of thermal medium body to the outside of heat transfer plate that supply with.
The conversion zone of above-mentioned plate-type reactor can be divided into 2 with upper curtate, can change the catalyst layer thickness of being filled in each conversion zone by the interval of adjusting a pair of heat transfer plate.The structure that the catalyst layer thickness everywhere that is preferably conversion zone especially increases towards outlet from the inlet of the reacting material mixture supplied with.In addition, can the outside that heat transfer plate is right be divided into the thermal medium body stream more than 2, supply with thermal medium body to this stream with the temperature that has nothing in common with each other.
The direction that is supplied to the reacting gas of above-mentioned plate-type reactor flows along heat transfer plate, and the thermal medium body is supplied with to the outside of a pair of heat transfer plate.The flow direction of this thermal medium body is not particularly limited, but in plant-scale reaction unit, need hold a large amount of catalyst usually, that a plurality of heat transfer plates are set is right, thereby with the flow direction of the reacting gas direction that meets at right angles be more suitably.
Usually the reacting dose in the reaction is accompanied by the generation maximum of the reaction heat of reaction in the intake section maximum of reacting gas, then reduces at the Way out of reacting gas.Change the heat that the average layer thickness of catalyst layer can more critically be controlled reaction and be produced by reaction by the interval of adjusting heat transfer plate, can prevent to be accompanied by the generation of heat spot of the rising of catalyst layer temperature, and can prevent the damage of catalyst.
In addition, by using above-mentioned plate-type reactor, can eliminate seen in the multi-tubular reactor to, the reduction of the yield of increase under the high condition of the processing load of the unit catalyst of reacting gas, the reaction gas pressure loss and the goal response product that accompanies with it.Further, can cut down with reactor in the rising of pressing supply that accompany, reacting gas etc. with the cost of energy of compressor.
Figure 41 shows the 1st concrete example of above-mentioned plate-type reactor.
The thin plate heat transfer plate (57) that thermal medium body stream (60-1,60-2 and 60-3) and catalyst layer (43) are kept apart is along deforming to change the thickness of catalyst layer (43) to the flow direction of outlet (59) from reaction gas inlet (58).Herein, the average layer thickness of catalyst layer for and the plate that records of the rectangular direction of the flow direction of reacting gas between distance.
The thickness that is formed at the catalyst layer (43) between a pair of heat transfer plate (57) forms each conversion zone (S1, S2 and S3) corresponding to each thermal medium body stream (60-1,60-2 and 60-3).(61) be thermal medium body supply port.Need to prove, in above-mentioned, conversion zone is made as 3, but this is an example, the number of conversion zone and indefinite.
In addition, in heat transfer plate (57), can use flat board, through embossing processing so that it has concavo-convex buckplate or the ripple plate through being shaped with the rectangular direction of the flow direction of reacting gas.If consider the heat transfer efficiency between reacting gas and the thermal medium body, then suitable buckplate or the ripple plate shape used.Herein, in the 1st concrete example, the average layer thickness of using catalyst layer under the situation of embossing processing or ripple plate in heat transfer plate (57) is with as shown in the formula regulation.
(formula) [average layer thickness of catalyst layer]=[volume of catalyst layer] ÷ [length of heat transfer plate (wide) (perpendicular to the length of the direction of paper among Figure 41)] ÷ [length of the flow direction of the reacting gas of heat transfer plate]
Herein, [volume of catalyst layer] is as follows: make a pair of heat transfer plate that forms catalyst layer keep vertical with respect to ground, and (bottom of each conversion zone) is provided with lid in the bottom, and in the space of a pair of heat transfer plate clamping, inject liquid or the bead below the diameter 1mm such as water, at this moment, be full of the volume of the following bead of liquid such as this needed water in space or diameter 1mm, be the volume of catalyst layer.
Second mode as above-mentioned plate-type reactor, can enumerate following plate-type reactor: promptly, in described plate-type reactor, make by figuration for circular arc, elliptic arc, rectangle or a polygonal part be main constitutive requirements continuous pattern 2 of ripple plates relatively to, and the convex surface part of this two ripples plate is bonded with each other forms thermal medium body stream more than 2, obtain heat transfer plate, make a plurality of arrangements of resulting heat transfer plate and make the ripple plate convex surface part of adjacent heat transfer plate relative with concave surface portion to, form the catalyst layer of appointed interval.Herein, above-mentioned what is called " by figuration for being the ripple plate of the continuous pattern of main constitutive requirements " with circular arc, elliptic arc, rectangle or a polygonal part mean the ripple plate ripple to be shaped as with circular arc, elliptic arc, rectangle or a polygonal part be the continuous pattern (shape) of main constitutive requirements.
In the above-mentioned plate-type reactor, be the shape of circular arc, elliptic arc, rectangle or the polygonal part of ripple plate, can change the thickness of catalyst layer to the exit by the inlet of the reacting gas that is supplied to catalyst layer by changing by figuration.In addition, in the above-mentioned plate-type reactor, conversion zone can be split into the field more than 2, can make the conversion zone that is split into 2 above fields corresponding with the varied in thickness of above-mentioned catalyst layer.Further, in 2 above conversion zones after cutting apart, the independent thermal medium body of adjusting through temperature of supplying with carries out heat extraction to the heat that is generated by catalytic gas phase oxidation reaction across heat transfer plate, can independently control the temperature in the catalyst layer.
The direction of reacting gas that is supplied to above-mentioned plate-type reactor is along the flows outside of heat transfer plate, and the thermal medium body is supplied to the inboard of a pair of heat transfer plate.The flow direction of this thermal medium body is right angle orientation, promptly mobile with the direction of cross flow with respect to flowing of reacting gas.
Usually the reacting dose in the reaction is in the intake section maximum of reacting gas, and the reaction heat maximum of following reaction to produce is in the Way out minimizing of reacting gas.In order to carry out the heat extraction of this reaction heat effectively, preferably change the concaveconvex shape of the employed ripple plate of a heat transfer plate and adjacent heat transfer, the gap of adjusting two heat transfer plates makes the average layer thickness of catalyst layer change.By changing the average layer thickness of catalyst layer, can more critically control reaction, along with the rising of catalyst layer temperature, the prevention heat spot can prevent the damage of catalyst.
Figure 42 shows the 2nd concrete example of above-mentioned plate-type reactor.
As shown in figure 42, for heat transfer plate (57), being deformed into 2 thin plates with circular, ellipse, rectangle or a polygonal part is the continuous pattern of main constitutive requirements, (with mirror) is engaged in the opposite direction Face to face each other, forms thermal medium body stream (60-1,60-2,60-3).In addition, with a pair of heat transfer plate (57) stagger each other be equivalent to thermal medium body stream half distance ground relatively to, form the gap, to formed gap catalyst filling, form catalyst layer (43).Further, a pair of heat transfer plate (57) has the reaction gas outlet (59) that imports the reaction gas inlet (58) and the derivation reacting gas of reaction mixture gas body to catalyst layer (43).
In the above-mentioned thermal medium body stream, the cross sectional shape of each stream (sectional area) difference, the width maximum of thermal medium body stream (60-1).Under the situation of the width maximum of thermal medium body stream (60-1), the interval of adjacent above-mentioned heat transfer plate (57) is constant, thereby the ripple plate convex surface part of adjacent heat transfer and concave surface portion opposite face and the interval (A) (being the bed thickness of catalyst layer (43)) that forms is the narrowest.By thermal medium body stream (60-2) thermotropism dielectric stream (60-3), the width of thermal medium body stream reduces successively, with the thickness increase of this corresponding catalyst layer of thermal medium body stream (43).Thereby in thermal medium body stream (60-1,60-2 and 60-3) corresponding catalyst layer (43), the average layer thickness difference of each catalyst layer can form different 2 the above conversion zones (S1, S2 and S3) of average layer thickness of catalyst layer.
Herein, the average layer thickness of catalyst layer be meant in each catalyst layer of each conversion zone (S1, S2 and S3) with the rectangular direction of the flow direction of reacting gas on the mean value at the above-mentioned interval (A) measured.In the 2nd concrete example, use calculating formula shown below to stipulate.
(formula) [average layer thickness of catalyst layer]=[volume of catalyst layer] ÷ [length of heat transfer plate (wide) (perpendicular to the length of the direction of paper among Figure 42)] ÷ [length of the flow direction of the reacting gas of heat transfer plate]
Herein, [volume of catalyst layer] is as lower volume: make a pair of heat transfer plate that forms catalyst layer keep vertical with respect to ground, and (bottom of each conversion zone) is provided with lid in the bottom, in the space of a pair of heat transfer plate clamping, inject liquid or the beades below the diameter 1mm such as water, at this moment, be full of the volume of the following bead of liquid such as this needed water in space or diameter 1mm.
Need to prove, hereinbefore, conversion zone is decided to be 3, but this only is an example, the number and the indefinite of conversion zone in the 3rd manufacture method of reaction product.
Formation based on the heat transfer plate (57) that uses in the 2nd concrete example of Figure 43 to above-mentioned plate-type reactor is described in more detail.Figure 43 shows following heat transfer plate: will be deformed into circular arc, elliptic arc, rectangle or a polygonal part be main constitutive requirements continuous pattern 2 of ripple plates relatively to, and the protuberance of this two ripples plate is bonded with each other, thereby form thermal medium body stream more than 2.
The size of thermal medium body stream and the average layer thickness of catalyst layer are stipulated with (L) and the wave height (H) of the period of wave that is equivalent to the ripple plate.At this moment, be preferably 10～100mm, 20～50mm more preferably period of wave (L).On the other hand, highly (H) is preferably 5～50mm, 10～30mm more preferably.
This heat transfer plate is the heat transfer plate of pair of parallel, and stagger each other be equivalent to thermal medium body stream half distance (L/2) relatively to, form the gap, to this gap catalyst filling, form catalyst layer.
The thickness of catalyst layer is regulated with the cycle (L) and the height (H) of thermal medium body stream by the interval (P) that changes this parallel a pair of heat transfer plate.The interval P of a pair of heat transfer plate is generally 10～50mm, 20～50mm more preferably.
Among Figure 43, the shape of heat transfer plate is depicted with the part of circular arc, and this shape also can be for being the continuous pattern of main constitutive requirements with elliptic arc, rectangle, triangle or a polygonal part.By change the above-mentioned cycle (L) and the height (H) can precision control catalyst layer thickness well.In addition, catalyst layer thickness is a homogeneous on length (width) direction (direction vertical with paper) of heat transfer plate preferably.
In addition, the average layer thickness of above-mentioned catalyst layer is relevant with interval shown in Figure 43 (x), and this interval (x) is generally 0.7～0.9 times of average layer thickness of the catalyst layer of above-mentioned formula regulation.
The thin plate of the heat transfer plate of each reactor (57) uses thickness of slab as below the 2mm, suitably be the steel plate below the 1mm.
The length of the reactant gas flow direction of heat transfer plate (57) is 0.5～10m (rice), be preferably 0.5～5m, 0.5～3m more preferably.According to size that can the conventional thin plate steel plate that obtains, be 1.5m when above in described length, also 2 plates can be engaged or be used in combination.
The length of the direction rectangular with the flow direction of the reacting gas degree of depth of the perpendicular direction of paper (in Figure 41 and 42 with) is not particularly limited, and uses 0.1～20m usually, preferably uses 3～15m.6～10m more preferably.Heat transfer plate (57) and configuration shown in Figure 43 be lamination similarly, and the sheet number of lamination without limits.In practice, determine by the needed catalytic amount of reaction, and be tens of to hundreds of.
The average layer thickness of the catalyst layer of above-mentioned each conversion zone is not particularly limited, and is preferably 4～50mm.In addition, the average layer thickness of the catalyst layer of above-mentioned each conversion zone is also different according to the load of reaction raw materials and the shape of catalyst (particle diameter etc.), in plate-type reactor shown in Figure 41, be 4～18mm (more preferably 5～13mm) but preferred exemplary goes out the average layer thickness of the catalyst layer of conversion zone (S1), the average layer thickness of the catalyst layer of the conversion zone (S2) after this conversion zone (S1) is 5～23mm (more preferably 7～17mm), the average layer thickness of the catalyst layer of the conversion zone (S3) after this conversion zone (S2) is 8～27mm (more preferably 10～22mm).
On the other hand, in plate-type reactor shown in Figure 42, be that (more preferably 7～15mm), the average layer thickness of the catalyst layer of the conversion zone (S2) after this conversion zone (S1) is that (more preferably 10～20mm), the average layer thickness of the catalyst layer of the conversion zone (S3) after this conversion zone (S2) is 12～30mm (more preferably 15～25mm) to 7～25mm to 5～20mm but preferred exemplary goes out the average layer thickness of the catalyst layer of conversion zone (S1).
In addition, the average layer thickness of the catalyst layer of these 2 above conversion zones preferably increases to the position of the direction of outlet successively according to the inlet from reacting gas.
Be that reaction raw materials at least a in the group formed of 3 and 4 the hydrocarbon and the tert-butyl alcohol is when carrying out oxidation particularly to being selected from by carbon number, the load of reaction raw materials is that 150 liter per hours are [through standard state (0 ℃ of temperature with respect to per 1 liter of catalyst, 101.325kPa) convert] under the above situation, and/or be that reaction raw materials at least a in the group formed of 3 and 4 unsaturated aliphatic aldehyde is when carrying out oxidation to being selected from by carbon number, the load of reaction raw materials is that 160 liter per hours are [through standard state (0 ℃ of temperature with respect to per 1 liter of catalyst, 101.325kPa) convert] under the above situation, the average layer thickness of the catalyst layer of the conversion zone (S1) that is connected with the reaction gas inlet (58) that imports the reaction mixture gas body to above-mentioned catalyst layer (43) is that 5～15mm (is preferably 7～12mm) especially, more preferably the average layer thickness of the catalyst layer of the conversion zone (S2) after this conversion zone (S1) is that (be preferably 10～15mm) especially, the average layer thickness of the catalyst layer of the conversion zone (S3) after this conversion zone (S2) is that 12～27mm (is preferably 15～20mm) especially to 7～17mm.
Under the situation of the average layer thickness of above-mentioned catalyst layer less than above-mentioned scope, when above-mentioned conversion zone S1 catalyst filling, bridge joint (Block リ Star ジ) takes place in catalyst granules in catalyst layer, and is attended by difficulties such as the filling time is elongated.Certainly, the smallest tier thickness of catalyst layer must be greater than the particle diameter of catalyst granules.Usually, the minimum thickness of catalyst layer is preferably more than 1.5 times of catalyst particle size.Thereby the average layer thickness of the catalyst layer of above-mentioned example suits when the particle diameter of catalyst granules is 3～5mm.
On the other hand, under the situation of the average layer thickness of catalyst layer greater than above-mentioned scope, become the reason that produces heat spot easily.Particularly if the situation that near the interior temperature of catalyst layer of the conversion zone (for example conversion zone (S3)) of the outlet of reacting gas rises, produces the heat spot phenomenon occurs, the conversion ratio that reaction raw materials perhaps occurs is compared too high such situation that approaches heat spot with optimum value, the phenomenon that achievement reduces, the yield of goal response product reduces then may occur reacting.Above-mentioned condition worsens, produces under the situation of heat spot, the catalyst damage also can occur.At this moment, the temperature limited reactions amount that need to reduce the thermal medium body also promotes removing of reaction heat, perhaps reduces the quantity delivered of reaction mixture gas body and reduces the load of reaction raw materials.
The details of the average layer thickness of above-mentioned catalyst layer is according to the variation of reacting dose and difference, and the inlet of self-catalysis agent layer (43) to outlet can change continuously, also can the ladder variation.If reactivity is inconsistent when considering the manufacturing catalyst, then the average layer thickness of the above-mentioned catalyst layer of ladder ground change can be guaranteed the free degree.
In addition, the number of cutting apart of above-mentioned conversion zone is preferably 2～5, preferably by the inlet of reacting gas towards outlet, the average layer thickness of the catalyst layer of each conversion zone increases.
Further, length for the flow direction of the reacting gas of the catalyst layer in each conversion zone, conversion ratio of considering reaction raw materials etc. is determined, for example, above-mentioned conversion zone is divided under 3 the situation, preferably use with respect to whole catalyst layer length, conversion zone (S1) part is 10%～55%, conversion zone (S2) part is 20%～65%, conversion zone (S3) part is 25%～70% catalyst layer length.In addition, the catalyst layer length of conversion zone (S3) part preferably changes according to the realization rate of the conversion ratio of reaction raw materials.
As mentioned above, in the reactor of practicality, under the situation that the processing load of the reaction raw materials of unit catalyst is improved, also need suitably to control the heat that generates by reaction, the generation of prevention heat spot, prevent the damage of catalyst, and improve the conversion ratio of reaction raw materials and the yield of goal response product.
In the 3rd manufacture method of reaction product, be that reaction raw materials at least a in the group formed of 3 and 4 the hydrocarbon and tert-butyl alcohol load when carrying out oxidation, reaction raw materials is more than 150 liter per hours [converting through standard state (0 ℃ of temperature, 101.325kPa)] with respect to per 1 liter of catalyst to being selected from by carbon number.To above-mentioned being selected from by carbon number is that reaction raw materials at least a in the group formed of 3 and 4 the hydrocarbon and tert-butyl alcohol load when carrying out oxidation, reaction raw materials preferably is 170～290 liter per hours [converting through standard state (0 ℃ of temperature, 101.325kPa)], especially preferably is 200～250 liter per hours [converting through standard state (0 ℃ of temperature, 101.325kPa)] with respect to per 1 liter of catalyst with respect to per 1 liter of catalyst.The load of above-mentioned reaction raw materials is the state that means more than 150 liter per hours [converting through standard state (0 ℃ of temperature, 101.325kPa)] that the processing load of the reaction raw materials of above-mentioned unit catalyst is improved with respect to per 1 liter of catalyst.
In addition, be that reaction raw materials at least a in the group formed of 3 and 4 unsaturated aliphatic aldehyde load when carrying out oxidation, reaction raw materials is more than 160 liter per hours [converting through standard state (0 ℃ of temperature, 101.325kPa)] with respect to per 1 liter of catalyst to being selected from by carbon number.To above-mentioned being selected from by carbon number is that reaction raw materials at least a in the group formed of 3 and 4 unsaturated aliphatic aldehyde load when carrying out oxidation, reaction raw materials preferably is 180～300 liter per hours [converting through standard state (0 ℃ of temperature, 101.325kPa)], especially preferably is 200～250 liter per hours [converting through standard state (0 ℃ of temperature, 101.325kPa)] with respect to per 1 liter of catalyst with respect to per 1 liter of catalyst.The load of above-mentioned reaction raw materials is the state that means more than 160 liter per hours [converting through standard state (0 ℃ of temperature, 101.325kPa)] that the processing load of the reaction raw materials of above-mentioned unit catalyst is improved with respect to per 1 liter of catalyst.
In the 3rd manufacture method of reaction product,, the thermal medium body temperature degree that is supplied to 2 above conversion zones is carried out independent control for the conversion ratio that improves reaction raw materials and the yield of goal response product.In addition, in the 3rd manufacture method of reaction product the unit of temperature be degree centigrade [℃].
In the 3rd manufacture method of reaction product, for the conversion ratio that improves reaction raw materials and the yield of goal response product, the temperature T (S1) of thermal medium body that is supplied to the conversion zone S1 of the inlet that approaches reacting material mixture most is higher than that to be supplied to the temperature T (S2) of thermal medium body of conversion zone S2 adjacent with conversion zone S1 and that be positioned at the downstream of reacting material mixture stream be important.
In addition, " T (S1)-T (S2) " more preferably more than 5 ℃, more preferably more than 10 ℃, be preferably more than 15 ℃ especially.In addition, " T (S1)-T (S2) " is preferably below 40 ℃.
In addition, be supplied to above-mentioned conversion zone S2, be positioned at the temperature of thermal medium body of conversion zone that reacting material mixture flows down trip for arbitrarily, can be identical with temperature T (S2), also can be different.But, be in the conversion zone of the scope more than 90% particularly at the conversion ratio that comprises reaction raw materials, preferably be lower than the temperature of temperature T (S2).
In the example of above-mentioned Figure 41 and 42 plate-type reactors of being put down in writing, when the temperature T (S1) that is supplied to the thermal medium body of conversion zone (S1) is higher than the temperature T (S2) of the thermal medium body that is supplied to conversion zone (S2), can improve the conversion ratio of reaction raw materials and the yield of goal response product.
In addition, in order further to improve the yield of goal response product, the temperature of thermal medium body that preferably is supplied to the conversion zone of the outlet that approaches reacting material mixture most be lower than be supplied to adjacent and be positioned at the temperature of thermal medium body of conversion zone of the upstream of reacting material mixture stream with this conversion zone.In addition, more preferably the absolute value of this temperature difference is more than 5 ℃, is preferably more than 10 ℃ especially.In addition, the absolute value of this temperature difference is preferably below 30 ℃.
In the 3rd manufacture method of reaction product, when the temperature of the thermal medium body that will be supplied to not specific any conversion zone S (j) be made as T (Sj), in the time of will being supplied to the temperature of thermal medium body of conversion zone S (j+1) adjacent with above-mentioned conversion zone S (j) and that be positioned at the downstream of reacting material mixture stream and being made as T (Sj+1), more preferably above-mentioned T (Sj) and above-mentioned T (Sj+1) satisfy the relation of T (Sj)＞T (Sj+1).
In the example of the plate-type reactor that above-mentioned Figure 41 and Figure 42 put down in writing, when the temperature that the temperature of the thermal medium body that will be supplied to conversion zone (S1) is made as T (S1), the temperature that will be supplied to the thermal medium body of conversion zone (S2) is made as T (S2), will be supplied to the thermal medium body of conversion zone (S3) is made as T (S3), preferably satisfy the relation of T (S 1)＞T (S2)＞T (S3).
In the 3rd manufacture method of reaction product, in order further to improve the yield of goal response product, the temperature that more preferably will be supplied to the thermal medium body of not specific any conversion zone S (j) is made as T (Sj), it is adjacent with above-mentioned conversion zone S (j) to be supplied to and the temperature of above-mentioned thermal medium body of conversion zone S (j+1) that be positioned at the downstream of reacting material mixture stream when being made as T (Sj+1), and above-mentioned T (Sj) and above-mentioned T (Sj+1) satisfy the relation of T (Sj)-T (Sj+1) 〉=5.In addition, further preferred T (Sj)-T (Sj+1) 〉=10, preferred especially T (Sj)-T (Sj+1) 〉=15.In addition, the value of T (Sj)-T (Sj+1) is preferably below 30.
As mentioned above, for the conversion ratio with reaction raw materials remains on the best, the temperature of thermal medium body is regulated.In the 3rd manufacture method of reaction product, the carrying out that promotes reaction in desire improved the temperature of thermal medium body of the conversion zone of the upstream that is supplied to the flow direction that is positioned at reacting material mixture and comes conditioned reaction when scheming the raising of reaction raw materials conversion ratio.Otherwise, when hope reduces too high conversion ratio, at first reduce the temperature of thermal medium body of the conversion zone in the downstream that is supplied to the flow direction that is positioned at reacting material mixture and come the conditioned reaction conversion ratio.
In the 3rd manufacture method of reaction product, be preferably more than 90% at the conversion ratio of the reaction raw materials in the reaction product exit of plate-type reactor, more preferably more than 95%, be preferably more than 97% especially.
The thermal medium body is supplied in 2 above conversion zones with optimum temperature respectively.At this moment, make direction that the thermal medium body flows preferably with the flow direction quadrature of reacting gas.
In addition, the temperature difference of the inlet temperature of thermal medium body and outlet temperature is preferably 0.5～10 ℃, more preferably 2～5 ℃.
Under the situation of plate-type reactor shown in Figure 42, in each thermal medium body stream (60-1,60-2,60-3), also can be per 1～2 above stream change flow, temperature and the flow direction of thermal medium body.In addition, in a conversion zone, the situation that also has per 1～2 above stream that the thermal medium body of uniform temp is flowed with equidirectional also has situation about flowing in the opposite direction.In addition, also the thermal medium body that is supplied to the thermal medium body stream of certain conversion zone and discharge may be supplied in the thermal medium body stream of identical or other conversion zone.
For the heat that is generated by reaction is carried out heat extraction and more reliably the temperature in the catalyst layer in the conversion zone is carried out independent control across above-mentioned heat transfer plate, it is very important that the temperature of the thermal medium body that is supplied to conversion zone is carried out stable control, and the temperature of thermal medium body preferably has separately independently temperature control device.For example, when the thermal medium body that is come out by conversion zone S (j+1) is back to the conversion zone S (j) of upstream, also, resupply to conversion zone S (j) preferably utilizing the temperature control device to adjust thermal medium body temperature degree T (Sj) afterwards.In addition, also can shunt the back or with collaborate laggard trip temperature adjustment from the thermal medium body of other conversion zone or the thermal medium body of different temperatures, be supplied to conversion zone S (j).
The temperature that is supplied to the thermal medium body of thermal medium body stream is preferably supplied with 200～600 ℃.Reaction raw materials is when to be selected from by carbon number be reaction raw materials at least a in the group formed of 3 and 4 the hydrocarbon and the tert-butyl alcohol, preferably to be supplied to each conversion zone with 250～450 ℃, more preferably 300～420 ℃.This reaction raw materials is under the situation of propylene, and the temperature that preferably is supplied to the thermal medium body of 2 above conversion zones is 250～400 ℃, more preferably 320～400 ℃.
On the other hand, reaction raw materials is when to be selected from by carbon number be reaction raw materials at least a in the group formed of 3 and 4 unsaturated aliphatic aldehyde, preferably to be supplied to each conversion zone with 200～350 ℃, more preferably 250～330 ℃.This reaction raw materials is under the situation of methacrylaldehyde, and the temperature that preferably is supplied to the thermal medium body of 2 above conversion zones is 250～320 ℃.
In same conversion zone, the temperature of preferred thermal medium body is basic identical, but can change in the scope that does not produce the heat spot phenomenon.
The flow that is supplied to the thermal medium body of thermal medium body stream is determined by heat of reaction and heat transfer impedance (Den Hot opposing).But for the heat transfer impedance, usually seldom because the resistance of heat transfer Chinese People's Anti-Japanese Military and Political College of the gas side of reacting gas has problems in the heat transfer impedance as the thermal medium body of liquid, but the interior liquidus speed of thermal medium body stream suitably adopts more than the 0.3m/s.In order to obtain as and value that do not have problems little with the impedance on the anti-thermal medium side of comparing of reaction gas side resistance of heat transfer, 0.5～1.0m/s is optimal.If excessive, then the power of the circulating pump of thermal medium body increases, and is not preferred from economic aspect.In addition, employed thermal medium body can use known material.
In the 3rd manufacture method of reaction product, reaction pressure is generally normal pressure～3,000kPa (kPa), be preferably normal pressure～1,000kPa (kPa), normal pressure～300kPa more preferably.
Embodiment
Use embodiment to carry out specific description below, but the present invention is not subjected to any restriction of embodiment.
(embodiment 1)
In first plate-type reactor, heat in the catalyst layer is given and accepted and can be carried out effectively, thereby as long as reaction for needing heat to give and accept, all can be suitable for for any raw material, catalyst, reaction, show herein and utilize oxygen that propylene is carried out oxidation to make methacrylaldehyde, acrylic acid reaction as embodiment.
When utilizing molecularity oxygen that propylene is carried out oxidation and makes methacrylaldehyde, according to following manufacturing catalyst of disclosed method such as Japanese kokai publication sho 63-54942 communique, the special fair 6-13096 communique of Japan, the special fair 6-38918 communiques of Japan.
(manufacturing of catalyst)
With 94 weight portion ammonium paramolybdate heating for dissolving in 400 parts by weight of purified water.In addition with 7.2 weight portion ferric nitrates (III), 25 weight portion cobalt nitrates and 38 weight portion nickel nitrate heating for dissolving in 60 parts by weight of purified water.These solution are fully stirred mixing simultaneously, obtain the solution of pulp-like.
Next, 0.85 weight portion borax and 0.36 weight portion potassium nitrate are dissolved in 40 parts by weight of purified water under heating, are added in the above-mentioned slurry.Adding 64 weight portion pelletized silicas subsequently stirs.Then adding the bismuth subcarbonate that 58 weight portions are compounded with 0.8 weight %Mg in advance mixes, behind this slurry heat drying, under air atmosphere, carry out heat treatment in 1 hour in 300 ℃, use make-up machine to spray the lozenge that ingot is shaped to diameter 4mm, height 3mm resulting granular solids, next carry out 4 hours fire at 500 ℃, obtain catalyst A.
Resulting catalyst A is the composite oxides with ratio of components of Mo (12) Bi (5) Ni (3) Co (2) Fe (0.4) Na (0.2) Mg (0.4) B (0.2) K (0.1) Si (24) O (x) (the composition x of oxygen is the value definite according to the state of oxidation of each metal).
The plate-type reactor A that uses plate-type reactor with Fig. 1 to have same formation carries out the oxidation reaction of propylene.Among the plate-type reactor A, to thickness is that the corrosion resistant plate of 1mm forms, has the heat transfer plate that plate 2 chip bondings after being shaped are formed, the major diameter of heat-transfer pipe 1 (L) is 40mm, the minor axis of heat-transfer pipe (H) is 20mm, the axle base of heat transfer plate (P) is 26mm, has a conversion zone, accommodates catalyst A.Utilize CCD laser extensometer ((strain) KEYENCE society makes LK-G152) that the shape of the plate after being shaped is measured, the plate after the result is shaped is with respect to the error deficiency ± 0.2mm of the design load that is shaped.In plate-type reactor A, heat transfer plate is configured for the mode of vertical direction according to it.
The design load of the distance between the surface of the heat transfer plate among the plate-type reactor A is to count 15mm based on the flange of the heat-transfer pipe of side's heat transfer plate and based on the distance between the recessed edge of the connecting portion of the heat-transfer pipe of the opposing party's heat transfer plate.For the distance between the surface of above-mentioned heat transfer plate, axial mensuration 3 places of heat-transfer pipe along axial mensuration 7 places of heat transfer plate, in the heat transfer plate, add up to and measure 21 places, the result is 17 places also at 81% of measuring point, and the difference of above-mentioned design load and measured value is in the 0.2mm.In addition, distance between the surface of heat transfer plate is to measure with accessory (gold utensil) by insert following two kinds of mensuration in the gap of heat transfer plate, and described two kinds of mensuration accessories are mensuration accessories that the mensuration pole member of diameter 1mm, length 15.2mm and 14.8mm at right angles has been installed in the position that the front end by the pole member of length 50cm, diameter 4mm plays 30mm.For plate-type reactor A, in the distance between the surface of heat transfer plate, the difference that measured value and design load are arranged is the situation of 0mm.
Thermal medium uses Nitrates mixture fuse salt (Na イ タ one).Thermal medium is adjusted into the temperature that is fit to conversion zone, is supplied to heat-transfer pipe.Thermal medium is to supply with more than the per second 0.7m by the flow velocity of thermal medium.
As unstrpped gas, be that the reaction raw materials mist of 9.5 moles of %, 9.5 moles of % of water concentration, 14.2 moles of % of oxygen concentration, nitrogen 66.8% is supplied to plate-type reactor so that the pressure of reactor inlet is 0.07MPaG (MPa gauge pressure) with the ratio of 6750 liters (standard state) per hour with density of propylene.
The length and the distance between heat transfer plate (P) of the major diameter of the heat-transfer pipe among the plate-type reactor A, minor axis, conversion zone are listed in table 1.In addition the temperature of thermal medium, the peak temperature of conversion ratio, selection rate and catalyst layer as raw material propylene (PP) are listed in table 2, described selection rate obtains divided by propylene (PP) conversion ratio as the methacrylaldehyde (ACR) of object and the total yield of acrylic acid (AA).
[table 1]
Figure BPA00001229958200741
[table 2]
(embodiment 2)
Except that the axle base that makes heat transfer plate (P) for the 26.5mm, use the plate-type reactor B that has with plate-type reactor A same structure, at first adopt the condition identical to implement to react with embodiment 1.The measured value of the distance between surface in plate-type reactor B, heat transfer plate is the distance between the recessed edge of the flange of side's heat transfer plate and the opposing party's heat transfer plate, similarly to Example 1 above-mentioned distance is measured, the result also is that 16 places are 15.5 ± 0.2mm at 76% of measuring point.The difference that plate-type reactor B is equivalent to measured value and above-mentioned design load is the situation of+0.5mm.In this reaction, the peak temperature of catalyst layer is 419 ℃, and further increases, and therefore stops reaction for the time being.
The peak temperature of the catalyst layer of plate-type reactor B is identical with the peak temperature of catalyst layer among the embodiment 1, the temperature of thermal medium is reduced to 338 ℃, implement reaction in addition similarly to Example 1, the result is as shown in table 2, has obtained the reaction achievement equal with embodiment 1.
(embodiment 3)
Except that the axle base that makes heat transfer plate (P) for the 27.5mm, use the plate-type reactor C that has with plate-type reactor A same structure, at first adopt the condition identical to implement to react with embodiment 1.The measured value of the distance between surface in plate-type reactor C, heat transfer plate is the distance between the recessed edge of the flange of side's heat transfer plate and the opposing party's heat transfer plate, similarly to Example 1 above-mentioned distance is measured, the result also is that 18 places are 16.5 ± 0.2mm at 86% of measuring point.The difference that plate-type reactor C is equivalent to measured value and above-mentioned design load is the situation of+1.5mm.In this reaction, the peak temperature of catalyst layer is 442 ℃, and further increases, and therefore stops reaction for the time being.
For the peak temperature of the catalyst layer among the peak temperature of the catalyst layer that makes plate-type reactor C and the embodiment 1 identical, the temperature of thermal medium is reduced to 330 ℃, implement reaction in addition similarly to Example 1, the result is as shown in table 2 to have obtained the reaction achievement equal with embodiment 1.
(comparative example 1)
Except that the axle base that makes heat transfer plate (P) is 28.5mm, use the plate-type reactor D that has same structure with plate-type reactor A, at first adopt condition similarly to Example 3 to implement to react.In plate-type reactor D, the measured value of the distance between the surface of heat transfer plate is the distance between the recessed edge of the flange of side's heat transfer plate and the opposing party's heat transfer plate, similarly to Example 1 above-mentioned distance is measured, the result also is that 19 places are 17.5 ± 0.2mm at 90% of measuring point.The difference that plate-type reactor D is equivalent to measured value and above-mentioned design load is the situation of+2.5mm.In this reaction, the peak temperature of catalyst layer surpasses 450 ℃, and the possibility that causes runaway reaction is arranged, thereby stops reaction for the time being.Except that the temperature with thermal medium is reduced to 300 ℃, implement reaction similarly to Example 1, but conversion ratio is no more than 50%, reaction is not carried out.
(embodiment 4)
The plate-type reactor E that use has two conversion zones carries out the oxidation of propylene.In plate-type reactor E, first conversion zone is the structure identical with plate-type reactor B.Second conversion zone after first conversion zone is to be that the axle base of 400mm, heat transfer plate is the identical structure of plate-type reactor of 27.5mm with the minor axis (H) of heat-transfer pipe for the length of 16mm, conversion zone.
In first conversion zone of plate-type reactor E, the design load of the distance between the surface of heat transfer plate is the distance between the recessed edge of the flange of side's heat transfer plate and the opposing party's heat transfer plate, is 15.5mm.The difference that first conversion zone is equivalent to measured value and mean value in the distance between the surface of heat transfer plate is the situation of+0.5mm.In addition, in second conversion zone of plate-type reactor E, the design load of the distance between the surface of heat transfer plate is the distance between the recessed edge of the flange of side's heat transfer plate and the opposing party's heat transfer plate, is 18.5mm.In addition, similarly to Example 1 above-mentioned distance is measured, the result is 13 places also at 87% of measuring point, and measured value is 18.5 ± 0.2mm.The difference that second conversion zone is equivalent to measured value and mean value on the distance between the surface of heat transfer plate is the situation of+1.5mm.
In each conversion zone, for the peak temperature of the catalyst layer among the peak temperature that makes catalyst layer and the embodiment 1 identical, the temperature that makes thermal medium in first conversion zone is that the temperature of thermal medium is 328 ℃ in 330 ℃, second conversion zone, in addition, adopt the condition identical to implement to react with embodiment 1.Its result is as shown in table 2, has obtained excellent similarly to Example 1 reaction achievement.
(comparative example 2)
The plate-type reactor F that use has two conversion zones carries out the oxidation of propylene.In plate-type reactor F, first conversion zone is the structure identical with plate-type reactor D, and second conversion zone is identical with second conversion zone among the embodiment 4.The difference that first conversion zone among the plate-type reactor F is equivalent to measured value and above-mentioned design load for the situation of+2.5mm, the difference that second conversion zone among the plate-type reactor F is equivalent to measured value and above-mentioned design load similarly to Example 4 is+situation of 1.5mm.
Except that the temperature that makes thermal medium and embodiment 4 are identical, implement reaction with the condition identical with embodiment 1, its result, the peak temperature of catalyst layer surpasses 450 ℃, and the possibility that causes runaway reaction is arranged, thereby stops reaction for the time being.Except that the temperature with the thermal medium in first conversion zone is reduced to 300 ℃, implement reaction similarly to Example 1, but conversion ratio is no more than 50%, reaction is not carried out.
(embodiment 5)
As plate-type reactor,, make device shown in Figure 16 for filling test usefulness.6 heat transfer plates are set.The axial length (width of heat transfer plate) of heat-transfer pipe in the heat transfer plate is 5m.The latch for printed circuit of vent board (porous plate) is set in the bottom of heat transfer plate.The axial heat transfer plate height of heat transfer plate from this vent board beginning is 1.88m, and the line part of no heat-transfer pipe forms 150mm upward from above-mentioned vent board.Dividing plate is provided with at interval with 50cm.Dividing plate is the device of shape shown in Figure 17, and its thickness of slab is 5mm.
Heat transfer plate is made in the following way: stainless steel (SUS304L) the system steel formability that with thickness of slab is 1mm is the consecutive shape of formed bead between circular-arc recess and recess for its cross sectional shape, and the above-mentioned bead in two steel plates after will being shaped is welded to one another, thereby produces heat transfer plate.The specification of heat-transfer pipe is shown in following table 3 in this heat transfer plate.In addition, in above-mentioned plate-type reactor, distance is 24mm between the above-mentioned line part in the adjacent heat transfer.
[table 3]
Major diameter (mm) Minor axis (mm) The heat-transfer pipe number
The 1st conversion zone 2a 50 20 12
The 2nd conversion zone 2b 40 16 11
The 3rd conversion zone 2c 30 10 23
In above-mentioned plate-type reactor, catalyst filling in the section that forms by adjacent heat transfer and dividing plate.Catalyst uses the following catalyst that obtains: preparation consists of the composite metal oxide powder of Mo (12) Bi (5) Co (3) Ni (2) Fe (0.4) Na (0.4) B (0.2) K (0.08) Si (24) O (x), with its moulding, be shaped to the cylindric of external diameter 4mm Ф, height 3mm, fire, obtain catalyst.Herein, Mo, Bi, Co, Ni, Fe, Na, B, K, Si, O are atomic symbol, the value of (x) of O (x) for determining by the state of oxidation of each metal oxide.
In the filling of catalyst, the vibrating feeder (conveyer) that the interval 50cm of use and dividing plate has same widths.(about 0.8～0.9L/min) filling speed is supplied with catalyst to above-mentioned zone with below 1L (liter)/per minute.In more detail, measure 11.6 liters catalyst, prepare 33 bags of catalyst that are sub-divided into respectively in the polybag, utilize above-mentioned vibrating feeder (conveyer) to be filled to each section.The theory of computation value of the packed height of being tried to achieve by the volume of each section is 182.5cm.
Thereafter, in order to measure the packed layer height, what make formed catalyst layer toply evenly measures the distance with the upper end of heat transfer plate, and the difference of the height of the heat transfer plate that begins by this distance and from above-mentioned vent board is determined packed height.11 places are carried out at this Determination of distance interval with 5cm in a section.The catalyst feed speed that depends on vibrating feeder (conveyer) has fluctuation, and the big situation of the temporary transient change of feed speed is also arranged.During the extreme deviation of feed speed, it is big that the catalyst layer height becomes, and bridge joint takes place sometimes, and the situation of overflowing from zone between heat transfer plate is also arranged; At this moment, take the latch for printed circuit that is installed on regional bottom, unload vent board, extract catalyst out, fill once more.For recharging, to implement 3 times then be sufficient if add up in ading up to 300 times filling operation.
According to the measurement result of filling floor height, the floor height and the theoretical value of catalyst layer differ ± 5cm in.The height of catalyst layer has ± 2.7% deviation with respect to the above-mentioned theory value.By this result as can be known, in above-mentioned plate-type reactor with dividing plate, by catalyst filling in above-mentioned each section, can be very equably to above-mentioned gap catalyst filling.
(embodiment 6)
The computational methods of the load of the yield of the selection rate of the conversion ratio of used reaction raw materials, goal response product, goal response product and reaction raw materials are as described below in the present embodiment of the 3rd manufacture method that relates to reaction product.
＜1〉conversion ratio [%] of reaction raw materials (propylene, methacrylaldehyde etc.)=
(being converted into the molal quantity of the reaction raw materials of other material in the reactor)/(being supplied to the molal quantity of the reaction raw materials of reactor) * 100
＜2〉selection rate of goal response product [%]=(molal quantity of the goal response product of reactor outlet)/(being converted into the molal quantity of the reaction raw materials of other material in the reactor) * 100
＜3〉yield of goal response product [%]=
(molal quantity of the goal response product of reactor exit)/(being supplied to the molal quantity of the reaction raw materials of reactor) * 100
＜4〉load of reaction raw materials [NL/Lhr]=
The per hour quantity delivered L[liter of reaction raw materials] [converting]/be supplied to catalyst for reaction amount L[liter through standard state]
Herein, so-called standard state refers to the state that is in 0 ℃ of temperature, pressure 101.325kPa (absolute pressure).
Utilizing molecularity oxygen that propylene is carried out catalytic gas phase oxidation when making acrylic acid, as be converted to methacrylaldehyde and acrylic acid leading portion catalyst by propylene, preparation consists of the metal oxide powder of Mo (12) Bi (5) Co (3) Ni (2) Fe (0.4) Na (0.4) B (0.2) K (0.08) Si (24) O (x), it is carried out moulding, obtain the cylindric beaded catalyst of external diameter 4mm Ф, height 3mm.Further, as methacrylaldehyde being converted to acrylic acid back segment catalyst, preparation consists of the metal oxide powder of Mo (12) V (2.4) Ni (15) Nb (1) Cu (1) Sb (59) Si (7) O (x), with this powder compacting, obtain the ring-type catalyst of external diameter 5mm Ф, internal diameter 2mm Ф and height 3mm.Herein, O (x) (x) is the value of being determined by the state of oxidation of each metal oxide.
In plate-type reactor, use the reactor of structure shown in Figure 42.With thin corrosion resistant plate (thickness of slab 1mm) 2 chip bondings of waveform shape, form the thermal medium body stream that reaction temperature is regulated usefulness.The cycle of waveform shape shown in Figure 43 (L), highly (H) and wave number are listed in table 4.
In the leading portion reactor, fill the leading portion catalyst, in backend reactors, fill the back segment catalyst, thereby form catalyst layer in a pair of waveform heat transfer plate behind this joint.For the catalyst layer in leading portion reactor and the backend reactors, all rise and be divided into conversion zone (S1), conversion zone (S2) and conversion zone (S3) according to the upstream of the specification of waveform shape autoreaction gas flow as shown in table 4 direction.1 pair of waveform heat transfer plate is be arranged in parallel as shown in figure 42, its interval (P shown in Figure 43) is adjusted into 26mm.The width of heat transfer plate is 114mm.
[table 4]
Figure BPA00001229958200791
Catalytic amount shown in the table 4 is following stereometry result, and this stereometry is to make each reactor vertical, at catalyst layer foot installing plate, and measure by top injection water.This catalytic amount is used for the calculating of the load of reaction raw materials.
As reaction raw materials, contain the reacting material mixture (reaction mixture gas body hereinafter referred to as) of 9.5 moles of % propylene by inlet (conversion zone (the S1)) feeding of leading portion reactor.In the reaction mixture gas body, except that propylene, also contain 15.2 moles of % oxygen, 65.9 moles of % nitrogen and 9.4 moles of % steam.
In the leading portion reactor shown in the table 4, fill above-mentioned leading portion catalyst, carry out the oxidation reaction of propylene.The thermal medium body use to be combined and to be ground the NeoSK-OIL (registration mark) 1400 that Tecnix (strain) society makes, carry out adjustment respectively after, be supplied to conversion zone (S1)～conversion zone (S3).It is more than the per second 0.7m that the quantity delivered of thermal medium body makes the flow velocity of thermal medium body.
It with density of propylene the reaction mixture gas body of 9.5 moles of % is supplied to reactor with the ratio of 5,670 liter per hours [converting through standard state (0 ℃ of temperature, 101.325kPa)] inlet.In addition, the temperature that is supplied to each conversion zone (S1), (S2) and thermal medium body (S3) is respectively 342 ℃, 329 ℃ and 329 ℃.The quantity delivered of propylene is 539 liter per hours [converting through standard state (0 ℃ of temperature, 101.325kPa)] (hereinafter being also referred to as NL/Hr).The pressure of reactor inlet is 0.109MPaG (MPa gauge pressure), and the inlet of the catalyst layer of reactor and the pressure differential of outlet (pressure loss) are very little, are 14kPa.
Utilize gas chromatography that exit gas is analyzed, propylene conversion is 97.2% as a result, acrylic acid yield is 10.1%, the yield of methacrylaldehyde is 81.7%.The load of propylene is 167 liter per hours [converting through standard state (0 ℃ of temperature, 101.325kPa)] (hereinafter being also referred to as NL/LHr).
(embodiment 7)
Except that the temperature that will be supplied to each conversion zone (S1), (S2) and thermal medium body (S3) is adjusted to respectively 360 ℃, 345 ℃ and 329 ℃, implement reaction similarly to Example 6.Utilize gas chromatography that exit gas is analyzed, as a result propylene conversion be 98.3%, the yield of acrylic acid and methacrylaldehyde add up to 92.7%.
(embodiment 8)
The quantity delivered of reaction mixture gas body is increased to 7,817 liter per hours [converting] through standard state (0 ℃ of temperature, 101.325kPa), and the temperature that will be supplied to each conversion zone (S1), (S2) and thermal medium body (S3) be adjusted to 342 ℃, 335 ℃ and 334 ℃ respectively, implement reaction in addition similarly to Example 6.The feed speed of propylene is 743NL/Hr.
Utilize gas chromatography that exit gas is analyzed, propylene conversion is 95.4% as a result, acrylic acid yield is 11.5%, the yield of methacrylaldehyde is 79.2%.The load of propylene is 231NL/LHr.The pressure of reactor inlet be the pressure loss of the catalyst layer of 0.134MPaG (MPa gauge pressure), reactor be 30kPa (kPa).
(embodiment 9)
The reactor outlet gas that embodiment 8 is obtained is supplied to backend reactors, and methacrylaldehyde is carried out oxidation, makes acrylic acid.Supply source as the molecularity oxygen that is used for oxidation reaction, with air with 2,186 per hour [convert] and nitrogen mixes with the leading portion reactor outlet gas with 680 liter per hours [converting through standard state (0 ℃ of temperature, 101.325kPa)], be supplied to backend reactors through standard state (0 ℃ of temperature, 101.325kPa).
The temperature that is supplied to each conversion zone (S1), (S2) and the thermal medium body (S3) of backend reactors is respectively 284 ℃, 278 ℃ and 278 ℃.The quantity delivered of thermal medium body makes that the interior flow velocity of thermal medium body stream of each conversion zone is more than the per second 0.4m.The pressure of backend reactors inlet is 0.097MpaG ((MPa gauge pressure), the pressure loss of the catalyst layer of reactor are 29kPa (kPa).
Utilize gas chromatography that exit gas is analyzed, the conversion ratio of methacrylaldehyde is 99.4% as a result, acrylic acid is 86.3% with respect to the yield of the propylene that is supplied to the leading portion reactor.The load of methacrylaldehyde is 201NL/LHr.
(embodiment 10～12 and comparative example 3 and 4)
Making the used reaction mixture gas body of reaction is the composition of 9.4 moles of % of propylene, 15.2 moles of % of oxygen, 65.9 moles of % of nitrogen and 9.5 moles of % of steam, supply with propylene with load 219NL/LHr, and the temperature that will be supplied to each conversion zone (S1), (S2) and thermal medium body (S3) is adjusted into the temperature shown in the table 2, in addition, implement reaction similarly to Example 6.Utilize the analysis result of the exit gas that gas chromatography analyzes to list in table 5.Next carry out the reaction more than 230 hours, conversion ratio and stable yield there is no the sign that demonstrates catalyst degradation.
[table 5]
Figure BPA00001229958200811
(embodiment 13 and comparative example 5)
The plate-type reactor that uses is above-mentioned leading portion reactor, with the cycle shown in the table 4 (L), highly (H), wave number and ripple plate P is identical at interval, but the width of heat transfer plate is 96mm.In this heat transfer plate-type reactor, fill above-mentioned back segment catalyst.Packed height is that 1.8m, catalytic amount are 2.5L (liter).
As a comparative example 5, prepare following tube-type reactor, that is, the stainless steel tubulation that uses internal diameter 27mm is as reaction tube, and filling back segment in this reaction tube is 1.8m with catalyst until packed height.Catalytic amount is 1.0L.
With above-mentioned plate-type reactor and tube-type reactor vertical fixing, by the air of top supply room temperature, measure inlet pressure and outlet pressure, obtain the pressure loss of catalyst layer.The results are shown in table 6.
[table 6]
Figure BPA00001229958200821
Throughput [NL/LHr] expression catalyst 1L (liter), per 1 hour gas delivery volume herein.In addition, the volume of gas uses the volume that converts through standard state (0 ℃, 101.325kPa).
Describe the present invention above with reference to detailed and specific embodiment, but for a person skilled in the art, obviously can apply various changes and correction not breaking away from the spirit and scope of the present invention.
The Japanese patent application (Japanese Patent Application 2008-327973) that the Japanese patent application (Japanese Patent Application 2008-091818) that the Japanese patent application of submitting in the Japanese patent application (Japanese Patent Application 2008-091298) that the application submitted to based on March 31st, 2008, on March 31st, 2008 (Japanese Patent Application 2008-091705), on March 31st, 2008 submit to and on December 24th, 2008 submit to is introduced this specification with the form of reference with above-mentioned application content.
Industrial applicibility
Plate-type reactor is in it is made, since the configured offset design load of heat transfer plate, the desired reaction achievement of anticipation when therefore in the plate-type reactor of reality, can not get designing. But, in first plate-type reactor and preparation method thereof, provide the admissible error of special provision heat transfer plate configuration and the fixing technology of heat transfer plate in this error range. Thus, first manufacture method by the reaction product in the situation of the change that is not attended by the plate-type reactor structure, heat medium temperature controlled, established the technology of the desired reaction achievement of plate-type reactor that is used for realization reality, and can expect significantly to enlarge the possibility that plate-type reactor utilizes in the industrial production based on the catalytic reaction product of gas phase. Therefore, according to the present invention, expectation is based on the further development in the manufacturing field of the catalytic reaction product of gas phase.
In addition, in plate-type reactor, sometimes carry out by the thickness of adjusting catalyst layer and control reaction. In such plate-type reactor, the uniform filling catalyst is more difficult in reactor monolith, but second plate-type reactor can rapidly, accurately and easily carry out the suitable filling of catalyst, and can expect setting, the maintenance care at plate-type reactor and make regular check in the significantly improving of operation.
In addition, second manufacture method according to reaction product, at supply response raw material in the plate-type reactor that is filled with catalyst, make this reaction raw materials react to make in the manufacture method of product, can expect to prevent the reduction of the reaction achievement that the fluctuation of catalyst occupied state causes, realize the further raising of the reaction achievement brought with the corresponding anticipation reaction achievement of catalyst performance and through the catalyst of improvement.
In addition, the 3rd manufacture method according to reaction product, at supply response raw material in the plate-type reactor that is filled with catalyst, make this reaction raw materials react to make in the manufacture method of product, when the processing load of the reaction raw materials that improves the unit catalyst, can prevent the increase of the pressure loss of the reacting gas by catalyst, and can prevent heat spot by the heat that control reaction suitably produces, can when preventing the catalyst damage, improve the yield of goal response product.
Therefore, industrial value of the present invention is remarkable.

Claims (31)

1. plate-type reactor, this plate-type reactor has the reaction vessel that is used for gaseous feed is reacted, is arranged side by side at 2 above heat transfer plates of described reaction vessel and the thermal medium feedway that is used for supplying with to described heat transfer plate the thermal medium of desired temperature
Described heat transfer plate comprises 2 above heat-transfer pipes that link with the periphery of cross sectional shape or ora terminalis,
Described thermal medium feedway is supplied with the device of thermal medium for the heat-transfer pipe of the heat transfer plate in being contained in reaction vessel;
Described plate-type reactor is characterised in that,
The design load of the distance between the surface of described heat transfer plate is 5～50mm, the difference of the measured value of the distance between described surface and described design load is-0.6～+ 2.0mm, distance between the surface of described heat transfer plate be relatively to described heat transfer plate between the gap in, with the direction of equidistant the quadrature of face that constitutes apart from axle by described heat transfer plate on distance.
2. plate-type reactor as claimed in claim 1 is characterized in that, the axial length of described heat transfer plate is below the 5m.
3. plate-type reactor as claimed in claim 1 or 2 is characterized in that, described plate-type reactor further has the sept that is used for forming appointed interval between described heat transfer plate.
4. as each described plate-type reactor of claim 1～3, it is characterized in that, described heat transfer plate is that two steel plates engage and form, and these two steel plates are shaped as, and a plurality of axles with heat transfer plate link to each other the cross sectional shapes of the described heat-transfer pipe shape that forms that is divided into two.
5. as each described plate-type reactor of claim 1～4, it is characterized in that the upstream side of the ventilation direction of the unstrpped gas of difference in described gap of the measured value of the distance between described surface and described design load is littler.
6. plate-type reactor as claimed in claim 5, it is characterized in that the raw material reaction rate in described unstrpped gas is that the difference of the measured value of the distance position, between described surface below 70% and described design load is less than described reactivity poor greater than the measured value of distance 70% position, between described surface and described design load.
7. as each described plate-type reactor of claim 1～6, it is characterized in that the total measurement (volume) in described gap is more than the 3L.
8. as each described plate-type reactor of claim 1～7, it is characterized in that, described plate-type reactor further has temperature measuring apparatus, and this temperature measuring apparatus is used to measure the temperature of the position more than 2 places of the catalyst layer that catalyst is filled in described gap and forms.
9. the manufacture method of a reaction product, this manufacture method is used and is provided with side by side in reaction vessel that 2 above heat transfer plates, the gap between heat transfer plate are filled with catalyst and the plate-type reactor that forms catalyst layer, and described manufacture method comprises and gaseous feed is supplied to described reaction vessel and the operation by described catalyst layer and to the operation of the thermal medium of 2 that constitute described heat transfer plate above heat-transfer pipes supply predetermined temperatures, and described manufacture method reacts unstrpped gas in the presence of described catalyst and generates the reaction product of gaseous state;
Described manufacture method is characterised in that, with each described plate-type reactor of claim 1～8 as described plate-type reactor;
Thermal medium is supplied to heat-transfer pipe, and the temperature of this thermal medium is that to make the peak temperature of described catalyst layer be the temperature of setting value of the peak temperature of the catalyst layer that sets when design of plate-type reactor.
10. the manufacture method of reaction product as claimed in claim 9 is characterized in that, the reaction of the raw material in the presence of catalyst in the unstrpped gas is exothermic reaction.
11. the manufacture method of reaction product as claimed in claim 10, it is characterized in that described reaction product is methacrylaldehyde and/or acrylic acid, MAL and/or methacrylic acid, maleic acid, phthalic acid, ethylene oxide, alkane, alcohol, acetone and phenol or butadiene.
12. the preparation method of a plate-type reactor, described manufacture method is used for making following plate-type reactor: this plate-type reactor has the reaction vessel that is used to gaseous feed is reacted, is arranged side by side at 2 above heat transfer plates of described reaction vessel and the thermal medium feedway that is used for supplying with to described heat transfer plate the thermal medium of desired temperature
Described heat transfer plate comprises 2 above heat-transfer pipes that link with the periphery of cross sectional shape or ora terminalis,
Described thermal medium feedway is supplied with the device of thermal medium for the heat-transfer pipe of the heat transfer plate in being contained in reaction vessel;
This preparation method is characterised in that, it comprises following operation: the arranged spaced heat transfer plate that becomes design load with the distance between the surface of described heat transfer plate, heat-transfer pipe is engaged with the thermal medium feedway, distance between the surface of described heat transfer plate be relatively to heat transfer plate between the gap in, with the direction of equidistant the quadrature of face that constitutes apart from axle by described heat transfer plate on distance.
13. the preparation method of plate-type reactor as claimed in claim 12, it is characterized in that described heat transfer plate uses by two steel plates and engages the heat transfer plate that forms, these two steel plates are shaped as, a plurality of axles with heat transfer plate link to each other the cross sectional shapes of the described heat-transfer pipe shape that forms that is divided into two
Described steel plate after the shaping use error with respect to the design load of the shaping of steel plate be ± 0.5mm is with interior shaping steel plate.
14. the preparation method of plate-type reactor as claimed in claim 12 is characterized in that, described heat transfer plate uses the axial length of described heat transfer plate to be the heat transfer plate below the 5m.
15. preparation method as each described plate-type reactor of claim 12～14, it is characterized in that, described preparation method further comprises following operation: across being used for forming sept at interval between heat transfer plate, with in reaction vessel, dispose heat transfer plate before the thermal medium feedway engages, described interval is the interval that the distance between the surface of described heat transfer plate becomes design load.
16. having, a plate-type reactor, this plate-type reactor be used to the reaction vessel that reaction raw materials is reacted, the device that has heat-transfer pipe and be arranged side by side 2 above heat transfer plates in described reaction vessel and be used for supplying with the thermal medium body to described heat-transfer pipe;
The container that described reaction vessel is discharged from by the gap between adjacent heat transfer for the reaction raw materials of being supplied with;
Described heat transfer plate comprises the described heat-transfer pipe more than 2 that links with the periphery of cross sectional shape or ora terminalis;
Gap between adjacent heat transfer is filled with catalyst;
Described plate-type reactor is characterised in that it further has dividing plate, and this dividing plate is divided into hold the catalyst of being filled 2 with upper curtate with the gap between adjacent heat transfer along the ventilation direction in the reaction vessel.
17. plate-type reactor as claimed in claim 16 is characterized in that, described 2 identical with upper curtate volume separately.
18., it is characterized in that described 2 is 1～100L with upper curtate volume separately as claim 16 or 17 described plate-type reactors.
19. each the described plate-type reactor as claim 16～18 is characterized in that, described 2 is 2～25L with upper curtate volume separately.
20. each described plate-type reactor as claim 16～19, it is characterized in that, described plate-type reactor further has 2 above breather plugs, described breather plug has aeration, can be fixed on the end of each section, the end of inaccessible each section is to keep being contained in the catalyst in each section with freely loading and unloading.
21. plate-type reactor as claimed in claim 20 is characterized in that, described dividing plate and/or heat transfer plate have and are used to first fastener that card ends described breather plug,
Described breather plug has vent board, skirt section and second fastener, and described vent board has aeration, does not see through catalyst simultaneously; Described skirt section vertically is provided with respect to vent board in part or all of the periphery of vent board; Described second fastener is located at described skirt section, can freely block with described first fastener with loading and unloading and end.
22. each the described plate-type reactor as claim 16～21 is characterized in that, described 2 0.1～1m that are spaced apart with upper spacer.
23. a method, it is the method for each described plate-type reactor manufacturing reaction product of use claim 16～22, wherein:
This method comprises operation from the reaction product that the operation of the thermal medium body of desired temperature, gap supply response raw material and obtain between the adjacent heat transfer that is filled with catalyst discharge from described gap to described heat-transfer pipe that supply with;
Described reaction raw materials is an ethene; Being selected from by carbon number is at least a in the group formed of 3 and 4 the hydrocarbon and the tert-butyl alcohol or to be selected from by carbon number be at least a in the group formed of 3 and 4 unsaturated aliphatic aldehyde; Carbon number is the hydrocarbon more than 4; Dimethylbenzene and/or naphthalene; Alkene; Carbonyls; Cumene hydroperoxide; Butylene; Or ethylbenzene;
Described reaction product is an ethylene oxide; Carbon number is that 3 and 4 unsaturated aliphatic aldehyde and/or carbon number are 3 and 4 unrighted acid; Maleic acid; Phthalic acid; Alkane; Alcohol; Acetone and phenol; Butadiene; Or styrene.
24. it is that 3 and 4 unsaturated aliphatic aldehyde and carbon number are more than one the manufacture method of reaction product in the group formed of 3 and 4 unrighted acid that a manufacturing is selected from by unsaturated hydrocarbons, carbon number, this method is following (A) or method (B):
(A) supply response raw mix in possessing the plate-type reactor that is formed at the catalyst layer between the heat transfer plate, described reacting material mixture contains that to be selected from by carbon number be at least a and molecularity oxygen of the reaction raw materials in the group formed of 3 and 4 the hydrocarbon and the tert-butyl alcohol, described reaction raw materials is carried out catalytic gas phase oxidation, make that to be selected from by unsaturated hydrocarbons and carbon number be at least a reaction product in the group formed of 3 and 4 unsaturated aliphatic aldehyde;
(B) supply response raw mix in possessing the plate-type reactor that is formed at the catalyst layer between the heat transfer plate, described reacting material mixture contains that to be selected from by carbon number be at least a and molecularity oxygen of the reaction raw materials in the group formed of 3 and 4 unsaturated aliphatic aldehyde, described reaction raw materials is carried out catalytic gas phase oxidation, make that to be selected from by carbon number be at least a reaction product in the group formed of 3 and 4 unrighted acid;
This manufacture method is characterised in that:
Described plate-type reactor is split into 2 different above conversion zones of average layer thickness of catalyst layer, supply with the thermal medium body that independently carries out the temperature adjustment to described 2 above conversion zones, the heat that is generated by described oxidation is carried out heat extraction across described heat transfer plate, and the temperature in the described catalyst layer of independent control;
The temperature T (S1) that is supplied to the described thermal medium body of conversion zone S1 is higher than the temperature T (S2) of the described thermal medium body that is supplied to conversion zone S2, described conversion zone S1 approaches the inlet of described reacting material mixture most, described conversion zone S2 is adjacent with described conversion zone S1, and is positioned at the downstream of described reacting material mixture stream;
To described being selected from by carbon number is that reaction raw materials at least a in the group formed of 3 and 4 the hydrocarbon and tert-butyl alcohol load when carrying out oxidation, described reaction raw materials is more than 150 liter per hours [converting through standard state (0 ℃ of temperature, 101.325kPa)] with respect to per 1 liter of catalyst;
To described being selected from by carbon number is that reaction raw materials at least a in the group formed of 3 and 4 unsaturated aliphatic aldehyde load when carrying out oxidation, described reaction raw materials is more than 160 liter per hours [converting through standard state (0 ℃ of temperature, 101.325kPa)] with respect to per 1 liter of catalyst.
25. manufacture method as claimed in claim 24, it is characterized in that, when the temperature of the thermal medium body that will be supplied to not specific any conversion zone S (j) is made as T (Sj), in the time of will being supplied to the temperature of described thermal medium body of conversion zone S (j+1) adjacent with described conversion zone S (j) and that be positioned at the downstream of reacting material mixture stream and being made as T (Sj+1), described T (Sj) and described T (Sj+1) satisfy the relation of T (Sj)-T (Sj+1) 〉=5.
26., it is characterized in that the number of described conversion zone is 2～5 as claim 24 or 25 described manufacture methods, towards outlet, the average layer thickness of the catalyst layer of each conversion zone increases by the inlet of reacting material mixture.
27. each described manufacture method as claim 24～26, it is characterized in that, be selected from by carbon number to be reaction raw materials at least a in the group formed of 3 and 4 the hydrocarbon and tert-butyl alcohol load when carrying out oxidation, described reaction raw materials, to be 170～290 liter per hours [converting] to described through standard state (0 ℃ of temperature, 101.325kPa) with respect to per 1 liter of catalyst.
28. each described manufacture method as claim 24～27, it is characterized in that, be selected from by carbon number to be reaction raw materials at least a in the group formed of 3 and 4 unsaturated aliphatic aldehyde load when carrying out oxidation, described reaction raw materials, to be 180～300 liter per hours [converting] to described through standard state (0 ℃ of temperature, 101.325kPa) with respect to per 1 liter of catalyst.
29. each the described manufacture method as claim 24～28 is characterized in that, is more than 90% at the conversion ratio of the reaction raw materials in the reaction product exit of described plate-type reactor.
30. each the described manufacture method as claim 24～29 is characterized in that described reaction raw materials is a propylene, the temperature that is supplied to the thermal medium body of described 2 above conversion zones is 320～400 ℃.
31. each the described manufacture method as claim 24～29 is characterized in that described reaction raw materials is a methacrylaldehyde, the temperature that is supplied to the thermal medium body of described 2 above conversion zones is 250～320 ℃.
CN2009801103159A 2008-03-31 2009-03-30 Plate type reactor, manufacturing method therefor, and reaction product manufacturing method using the plate type reactor Pending CN101977678A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102688725A (en) * 2012-07-02 2012-09-26 西南石油大学 Hot plate type reactor
CN103717301A (en) * 2011-06-06 2014-04-09 阿克马法国公司 Plate-type reactor with in-situ injection

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015122129A1 (en) * 2015-12-17 2017-06-22 L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Reactor for carrying out exo- or endothermic reactions
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006000707A (en) * 2004-06-15 2006-01-05 Mitsubishi Chemical Engineering Corp Catalytic reactor
CN1906148A (en) * 2003-12-23 2007-01-31 巴斯福股份公司 Preparation of (meth)acrolein and/or (meth)acrylic acid by heterogeneously catalyzed partial oxidation of C3 and/or C4 precursor compounds

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2285690C2 (en) * 2000-06-20 2006-10-20 Басф Акциенгезельшафт Method for preparing acrolein and/or acrylic acid
FR2824755B1 (en) * 2001-05-15 2003-08-15 Physiques Et Chimiques PLATE REACTOR AND ITS OPERATION IN AN EXOTHERMIC CATALYTIC PROCESS
JP4401644B2 (en) * 2002-11-22 2010-01-20 三菱化学エンジニアリング株式会社 Plate type catalytic reactor and method for producing (meth) acrylic acid, etc.
RU2356882C2 (en) * 2003-12-23 2009-05-27 Басф Акциенгезельшафт Method of monitoring and/or controlling process of producing (meth)acrolein and/or (meth)acrylic acid

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1906148A (en) * 2003-12-23 2007-01-31 巴斯福股份公司 Preparation of (meth)acrolein and/or (meth)acrylic acid by heterogeneously catalyzed partial oxidation of C3 and/or C4 precursor compounds
JP2006000707A (en) * 2004-06-15 2006-01-05 Mitsubishi Chemical Engineering Corp Catalytic reactor

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103717301A (en) * 2011-06-06 2014-04-09 阿克马法国公司 Plate-type reactor with in-situ injection
CN103717301B (en) * 2011-06-06 2016-06-22 阿克马法国公司 There is the plate-type reactor that original position is injected
CN102688725A (en) * 2012-07-02 2012-09-26 西南石油大学 Hot plate type reactor
CN102688725B (en) * 2012-07-02 2014-04-09 西南石油大学 Hot plate type reactor

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