CN104707540A - Manufacturing method for plate type reactor - Google Patents

Manufacturing method for plate type reactor Download PDF

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Publication number
CN104707540A
CN104707540A CN201510118088.1A CN201510118088A CN104707540A CN 104707540 A CN104707540 A CN 104707540A CN 201510118088 A CN201510118088 A CN 201510118088A CN 104707540 A CN104707540 A CN 104707540A
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plate
heat transfer
mentioned
heat
catalyst
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CN201510118088.1A
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Inventor
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 Rayon Co Ltd
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Mitsubishi Kasei Corp
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Priority claimed from JP2008327973A external-priority patent/JP6088120B2/en
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Publication of CN104707540A publication Critical patent/CN104707540A/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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Abstract

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

Description

The preparation method of plate-type reactor
The application is divisional application, the international application no of its original application is PCT/JP2009/056567, China national application number is 200980110315.9, the applying date is on March 30th, 2009, and denomination of invention is " manufacture method that plate-type reactor, its preparation method and use plate-type reactor manufacture reaction product ".
Technical field
The present invention relates to plate-type reactor, its preparation method and use above-mentioned plate-type reactor to manufacture the manufacture method of reaction product by gas phase haptoreaction, described plate-type reactor is used for along with the use heat release of catalyst or the reaction of heat absorption.
In addition, the present invention relates to plate-type reactor and to supply response raw material in the plate-type reactor being filled with catalyst, this reaction raw materials is reacted and manufacture the manufacture method of reaction product.
Background technology
As make under the existence of solid catalyst the raw material of gaseous state react the reaction product obtaining gaseous state gas phase haptoreaction in the reactor that uses, in the known reaction tube such as had in reaction vessel, the multi-tubular reactor of catalyst filling (such as, with reference to patent document 1) and more than 2 heat transfer plates in reaction vessel between the plate-type reactor (for example, referring to patent document 2 and 3) of gap-fill catalyst.
These reactors used in gas phase haptoreaction require to make with high accuracy usually.Such as, if the caliber error of the heat-transfer pipe of the formation heat transfer plate in the reaction tube in multi-tubular reactor or plate-type reactor is large, then partly can there is the part that heat extraction is deteriorated, at partially catalyzed oxidant layer runaway reaction, the deterioration of catalyst locally may occur.But, to make reactor with more high accuracy, then may need very a large amount of artificial, a large amount of steel in the making of reactor.
In multi-tubular reactor, by the steel pipe that service precision in reaction tube is high, the precision of reactor can be improved with comparalive ease.On the other hand, the heat-transfer pipe in plate-type reactor makes usually in the following way: in the multiple connected mode of the shape be divided into two by the cross sectional shape of heat-transfer pipe by steel formability, and is welded to one another by the flange in the steel plate after shaping, makes thus.In addition, in plate-type reactor, what the cross sectional shape of heat-transfer pipe or sectional dimension adjusted from the viewpoint of the thickness of the catalyst layer to the gap be formed between heat transfer plate or form usually determines.Thus, in the making of plate-type reactor, the various factors making the precision of plate-type reactor occur to reduce during steel plate generation warpage when can not get desired shape in the shaping of above-mentioned steel plate, after forming and when there is warpage due to the welding of steel plate etc. can cause being difficult to produce high-precision plate-type reactor, therefore sometimes can not carry out the control of reacting fully.
Therefore, the main difficulty in the form of the heat transfer plate in plate-type reactor and manufacture method is that the high accuracy of plate-type reactor makes.Heat-exchangers of the plate type has and plate-type reactor similar structures having in the heat transfer plate this point be made up of heat-transfer pipe, the worst error of the setting value of the distance between heat-exchangers of the plate type be it has been generally acknowledged that relative to heat transfer plate be about 3 ~ 5mm or its more than.
But be attended by the use heat release of catalyst or the gas phase haptoreaction of heat absorption, it is very important for carrying out tight control to reaction temperature.If the temperature of catalyst layer controls insufficient, then the yield of deterioration or goal response product that catalyst can occur reduces.Therefore, if the precision of plate-type reactor is low, such as, if large relative to the error of the setting value of the distance between heat transfer plate, then partly can there is the part that heat extraction is deteriorated, react out of control in partially catalyzed oxidant layer, the deterioration of catalyst, the yield reduction of reaction product can locally occur.On the other hand, if pay attention to the raising of plate-type reactor precision, then in the making of plate-type reactor, need very a large amount of artificial, a large amount of steel, in the manufacture of reaction product using such reactor, productivity ratio can reduce, likely can not be practical in the industry of reaction product manufactures.
Such as the gas phase contact oxidation reaction at propane, propylene or methacrylaldehyde, be attended by heat release or heat absorption and the reactor using the gas-phase reaction of granular solid catalyst used, such as there will be a known following plate-type reactor: this plate-type reactor having reaction vessel for making vapor reaction raw material react, having heat-transfer pipe and more than 2 heat transfer plates be disposed side by side in above-mentioned reaction vessel and the device to above-mentioned heat-transfer pipe supply thermal medium body; Above-mentioned reaction vessel is the container that the gas supplying is discharged by the gap between adjacent heat transfer, above-mentioned heat transfer plate comprises the above-mentioned heat-transfer pipe of more than 2 be connected with the periphery of cross sectional shape or ora terminalis, gap-fill between adjacent heat transfer has catalyst (such as, see patent document 3).
Such plate-type reactor has the catalyst layer of more than 2 in the gap be formed between adjacent heat transfer usually, and the contact of heat transfer plate and catalyst is excellent, thus efficiency can manufacture a large amount of product well by above-mentioned gas-phase reaction, it is excellent from this viewpoint.
On the other hand, in above-mentioned gas-phase reaction, from the viewpoint of controlling gas-phase reaction, wish the occupied state homogenising of catalyst.In plate-type reactor, catalyst is filled with stratiform by the gap between adjacent heat transfer, thus be difficult to regularly (certain To) catalyst filling in above-mentioned each gap and all in gap, it is desirable to develop can in above-mentioned gap the technology of uniform filling catalyst.
In addition, deterioration occurs the partially catalyzed agent when catalyst is not filled in above-mentioned gap regularly or in above-mentioned gap, need whole catalyst in its gap to take out the filling again carrying out catalyst.Therefore, it is desirable to develop the technology that easily can adjust the occupied state of the catalyst in above-mentioned gap.
At present, utilizing catalytic gas phase oxidation reaction to manufacture in the manufacture method of the product such as unrighted acid, from the viewpoint of industrialness and practicality, the multi-tubular reactor of tubing heat exchanger shape is used.In the manufacture method of product using this multi-tubular reactor, solid catalyst is filled in the inner side of the reaction tube of multi-tubular reactor, make in the outside of reaction tube to circulate through temperature controlled thermal medium body, utilize this thermal medium body to control the temperature inside reaction tube.
When using above-mentioned multi-tubular reactor to manufacture the product such as unrighted acid, when wanting the manufacture increasing product, sometimes need the number increasing reaction tube according to the increase of manufacture.But in this case, it is also possible that reaction tube reaches tens thousand of, exceeds the making limit of multi-tubular reactor sometimes.Exceed when making limit, the fact has to have the reaction series of more than 2.
On the other hand, in the reaction tube number or reactor of regulation, sometimes need the processing load amount improving unit catalyst to guarantee desired manufacture.The reaction heat now produced in each reaction tube increases, and the thermal medium body that can produce not by circulating outside reaction tube carries out the situation suitably controlled to the temperature inside reaction tube.When not carrying out suitably controlling to the temperature inside reaction tube, the temperature remaining on the partially catalyzed agent inside reaction tube significantly rises (hereafter also referred to as heat spot (hot spot)).When the temperature of this partially catalyzed agent goes beyond the limit, partially catalyzed agent damages, and the durability period of catalyst shortens.
When damage occurs in partially catalyzed agent, need the production of the product stopping using this reactor, carry out catalyst exchange.That is, during exchange catalysts, the production of product stops, and produces and is difficult to guarantee the significant problems such as desired manufacture.In addition, even if seriously do not arrive the degree of catalyst exchange, due to the generation of heat spot, be also difficult to maintain suitable reaction condition, the problem such as the reaction achievement variation of catalyst, the productive rate reduction of goal response product can be produced.
In addition, in patent document 4 and 5, propose and use above-mentioned multi-tubular reactor to the method for carrying out catalytic gas phase oxidation reaction as the propylene of reaction raw materials or methacrylaldehyde under the state of the processing load amount improving unit catalyst.But there is following shortcoming: due to reaction tube used in multi-tubular reactor to be radius the be pipe of 20 ~ 30 millimeters, and use from the entrance of reacting fluid (general names of the mixture of reacting material mixture, reaction product etc.) to exporting the identical reaction tube of caliber, thus under the condition that the processing load amount of the unit catalyst of reacting fluid is high, the pressure loss of reacting fluid is large, pressure increase in reactor, result is that the productive rate of goal response product reduces.Further, along with the rising of pressing in reactor, the energy for the compressor of supply response fluid etc. increases, except unfavorable to the productive rate of goal response product, also unfavorable in cost.
As the method solved the problem, there is motion to propose to have the reactor for contact vapor-phase oxidation of heat-exchangers of the plate type structure.Such as, in patent document 2, propose between 2 heat transfer plates catalyst filling, board-like catalyst reaction equipment to the outside supply thermal medium body of heat transfer plate.In addition, following board-like hydrogen-catalyst reactor is proposed: making by figuration is that 2 ripple plates of circular arc or elliptic arc are relative in patent document 3, be formed with the multiple assortment of heat transfer plate of more than 2 thermal medium body streams by by making the convex surface part of this two ripples plate be bonded with each other and make the ripple plate convex surface part of adjacent heat transfer relative with concave part, thus forming the catalyst layer of predetermined space.
In above-mentioned motion, although describe the structure of plate-type reactor and its application in catalytic gas phase oxidation reaction, but there is no any mentioning for suitably controlling to react the heat that generates with the method for preventing heat spot and improving the productive rate of goal response product simultaneously.Particularly, there is no any mentioning for suitably controlling to react the heat generated when improving the processing load amount of unit catalyst with the method for the productive rate and manufacture that prevent the generation of heat spot, prevent the damage of catalyst and improve goal response product.
Patent document 1: Japanese Unexamined Patent Publication 2004-000944 publication
Patent document 2: Japanese Unexamined Patent Publication 2004-167448 publication
Patent document 3: Japanese Unexamined Patent Publication 2004-202430 publication
Patent document 4: Japanese Unexamined Patent Application Publication 2003-514788 publication
Patent document 5: Japanese Unexamined Patent Application Publication 2002-539103 publication
Summary of the invention
The invention provides can to prevent from reacting in the manufacture of reaction product out of control and can be used in the plate-type reactor of the manufacture of large-duty reaction product.
In addition, the invention provides use plate-type reactor to carry out preventing in the manufacture of reaction product to react out of control and make the method for reaction product with high production rate.
In addition, the invention provides can the plate-type reactor of gap-fill catalyst evenly and easily between adjacent heat transfer.
Further, the invention provides can gap-fill catalyst evenly and easily between adjacent heat transfer and easily can adjust the plate-type reactor of the occupied state of the catalyst in above-mentioned gap.
Further, the invention provides a kind of method of novelty, it is supply response raw material this reaction raw materials is reacted manufacture the manufacture method of reaction product in the plate-type reactor being filled with catalyst, in described manufacture method, even if improve when the processing load amount of the reaction raw materials of unit catalyst, also the increase of the pressure loss of the reacting gas by catalyst can be prevented, and by suitably controlling by the heat of reaction generation to prevent the generation of heat spot, and improve the yield of goal response product while preventing catalyst from damaging.
The invention provides following technology: namely,-0.6 ~+2.0mm is set in by the range of allowable error of the design load by the distance between the surface relative to heat transfer plate, thus do not control to cause obstacle to the temperature of plate-type reactor, do not rely on the use of low activity catalyst and the dilution of catalyst and the manufacturing cost of plate-type reactor maintained low cost, utilizing industrial favourable method to manufacture valuable product simultaneously.
Namely, the invention provides following plate-type reactor: this plate-type reactor having reaction vessel for making gaseous feed react, being disposed side by side on more than 2 heat transfer plates in above-mentioned reaction vessel and the thermal medium feedway for the thermal medium to the desired temperature of above-mentioned heat transfer plate supply, above-mentioned heat transfer plate comprises more than 2 heat-transfer pipes linked with the periphery of cross sectional shape or ora terminalis, and above-mentioned thermal medium feedway is the device of the heat-transfer pipe supply thermal medium to the heat transfer plate be 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 measured value of the distance between above-mentioned surface and the difference of above-mentioned design load are-0.6 ~+2.0mm (hereafter also referred to as " the first plate-type reactor "), distance between the surface of above-mentioned heat transfer plate is in the gap between relative above-mentioned heat transfer plate, the distance on the direction orthogonal with apart from equidistant, the face be made up of the axle of above-mentioned heat transfer plate.
In addition, the invention provides the first plate-type reactor, wherein, the length of the axis of above-mentioned heat transfer plate is preferably below 5m, more preferably below 2m.
In addition, the invention provides the first plate-type reactor, this first plate-type reactor preferably has the sept for forming appointed interval between above-mentioned heat transfer plate further.
In addition, the invention provides the 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 multiplely the shape that the cross sectional shape of above-mentioned heat-transfer pipe is divided into two is connected with the axle of heat transfer plate.
In addition, the invention provides the first plate-type reactor, the upstream side in the ventilation direction of the unstrpped gas in the measured value of the distance wherein between preferred above-mentioned surface and the gap of the difference of above-mentioned design load between heat transfer plate is less.
In addition, the invention provides the first plate-type reactor, wherein preferred in above-mentioned raw materials gas in raw material reaction rate be the position of less than 70%, the measured value of distance between above-mentioned surface and the difference of above-mentioned design load be less than and be greater than the measured value of the distance between the position of 70%, above-mentioned surface and the difference of above-mentioned design load in above-mentioned reactivity.
In addition, the invention provides the first plate-type reactor, wherein the total measurement (volume) in preferred above-mentioned gap is more than 3L.
In addition, the invention provides the first plate-type reactor, wherein preferably above-mentioned first plate-type reactor has temperature measuring apparatus further, this temperature measuring apparatus for measure the catalyst layer formed in above-mentioned gap by packed catalyst 2 places more than the temperature of position.
In addition, the invention provides the manufacture method of reaction product, this manufacture method is used in reaction vessel and is provided with more than 2 heat transfer plates side by side, gap-fill between heat transfer plate has catalyst and forms the plate-type reactor of catalyst layer, above-mentioned manufacture method comprises and gaseous feed is supplied to above-mentioned reaction vessel and by the operation of above-mentioned catalyst layer and to the operation of thermal medium of more than 2 heat-transfer pipes supply predetermined temperatures forming above-mentioned heat transfer plate, this manufacture method makes unstrpped gas react and generate the reaction product of gaseous state under the existence of above-mentioned catalyst; In this manufacture method, plate-type reactor of the present invention is used as above-mentioned plate-type reactor; Thermal medium is supplied to heat-transfer pipe (hereafter also referred to as " the first manufacture method of reaction product "), the temperature of thermal medium is the temperature of the setting value of the peak temperature of the catalyst layer that to make the peak temperature of above-mentioned catalyst layer be plate-type reactor set when designing.
In addition, the invention provides the first manufacture method of reaction product, the reaction of the raw material wherein in preferred unstrpped gas is in the presence of a catalyst exothermic reaction.
In addition, the invention provides the 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 for making following plate-type reactor: this plate-type reactor has the reaction vessel for making gaseous feed react, be disposed side by side on more than 2 heat transfer plates in above-mentioned reaction vessel, and for the thermal medium feedway of the thermal medium to the desired temperature of above-mentioned heat transfer plate supply, above-mentioned heat transfer plate comprises more than 2 heat-transfer pipes linked with the periphery of cross sectional shape or ora terminalis, above-mentioned thermal medium feedway is the device of the heat-transfer pipe supply thermal medium to the heat transfer plate be contained in reaction vessel, wherein, this preparation method comprises following operation: the gap between relative heat transfer plate, the interval configuration heat transfer plate of design load is become with the distance between the surface of heat transfer plate, engaged with thermal medium feedway by heat-transfer pipe, the distance between the surface of described heat transfer plate is the distance on the direction orthogonal with equidistant, the face that distance is made up of the 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 the heat transfer plate engaged by two steel plates, these two steel plates are shaped as, multiplely with the axle of heat transfer plate, the shape that the cross sectional shape of above-mentioned heat-transfer pipe is divided into two to be connected, the above-mentioned steel plate after shaping use relative to the error of the design load of the shaping of steel plate be ± 0.5mm within shaping steel plate.
Or the invention provides the preparation method of above-mentioned plate-type reactor, wherein preferred above-mentioned heat transfer plate uses the length of the axis of above-mentioned heat transfer plate to be below 5m, is preferably the heat transfer plate of below 2m.
In addition, the invention provides the preparation method of above-mentioned plate-type reactor, wherein preferably this preparation method comprises following operation further: across the sept for forming interval between heat transfer plate, with the joint of thermal medium feedway before in reaction vessel, configure heat transfer plate, described interval be above-mentioned heat transfer plate surface between distance become the interval of design load.
Further, the present invention also provides plate-type reactor, wherein preferred gap in plate-type reactor between adjacent heat transfer along the circulating direction of reaction raw materials formed can 2 of containing catalyst with upper curtate, can catalyst filling regularly at each section.
In addition, the invention provides plate-type reactor, wherein preferred gap in plate-type reactor between adjacent heat transfer along the circulating direction of reaction raw materials formed can 2 of containing catalyst with upper curtate, filling and the taking-up of catalyst can be carried out further independently at each section.
Namely, the invention provides a kind of plate-type reactor, this plate-type reactor has reaction vessel for making reaction raw materials react, there is heat-transfer pipe and more than 2 heat transfer plates be disposed side by side in above-mentioned reaction vessel and for the device to above-mentioned heat-transfer pipe supply thermal medium body; The container that above-mentioned reaction vessel is discharged by the gap between adjacent heat transfer for supplied reaction raw materials; Above-mentioned heat transfer plate comprises the above-mentioned heat-transfer pipe of more than 2 linked with the periphery of cross sectional shape or ora terminalis; Gap-fill between adjacent heat transfer has catalyst; In described plate-type reactor, the gap between this plate-type reactor has further by adjacent heat transfer is divided into 2 of the catalyst that accommodation is filled with the dividing plate of upper curtate (り cut by bodyguard) (hereafter also referred to as " the second plate-type reactor ") along the ventilation direction in reaction vessel.
In addition, the invention provides the second plate-type reactor, wherein preferably above-mentioned 2 identical with upper curtate volume separately.
In addition, the invention provides the second plate-type reactor, wherein preferably above-mentioned 2 with the respective volume of upper curtate for 1 ~ 100L.
In addition, the invention provides the second plate-type reactor, wherein preferably above-mentioned 2 with the respective volume of upper curtate for 2 ~ 25L.
In addition, the invention provides the second plate-type reactor, wherein preferred described plate-type reactor has more than 2 breather plugs further, and described breather plug has aeration, detachably be fixed on the end of each section, the end of inaccessible each section is to keep the catalyst be contained in each section.
In addition, the invention provides the second plate-type reactor, wherein preferably aforementioned barriers and/or heat transfer plate have the first fastener for engaging above-mentioned breather plug; Above-mentioned breather plug has vent board, skirt section and the second fastener, and above-mentioned vent board has aeration, simultaneously not through catalyst; Above-mentioned skirt section is vertically arranged relative to vent board in part or all of the periphery of vent board; Above-mentioned second fastener is located at above-mentioned skirt section, detachably engages with above-mentioned first fastener.
In addition, the invention provides the second plate-type reactor, wherein preferably above-mentioned 2 be spaced apart 0.1 ~ 1m with upper spacer.
In addition, the invention provides a kind of method, it is the method that use second plate-type reactor manufactures reaction product,
Wherein, the method comprise operation from the thermal medium body to the desired temperature of above-mentioned heat-transfer pipe supply, discharge from above-mentioned gap with the operation obtaining reaction product to the gap supply response raw material between the adjacent heat transfer being filled with catalyst;
Above-mentioned reaction raw materials is ethene; Be selected from by carbon number be 3 and 4 hydrocarbon and the group that forms of the tert-butyl alcohol at least one or at least one in the group that forms of unsaturated aliphatic aldehyde that to be selected from by carbon number be 3 and 4; Carbon number is the hydrocarbon of more than 4; Dimethylbenzene and/or naphthalene; Alkene; Carbonyls; Cumene hydroperoxide; Butylene; Or ethylbenzene;
Above-mentioned reaction product is ethylene oxide; Carbon number be 3 and 4 unsaturated aliphatic aldehyde and/or carbon number be the unrighted acid of 3 and 4; Maleic acid; Phthalic acid; Alkane; Alcohol; Acetone and phenol; Butadiene; Or styrene (hereafter also referred to as " the second manufacture method of reaction product ").
Further, the present inventor conducts in-depth research to solve above-mentioned problem, supply response raw material in the plate-type reactor of different more than 2 conversion zones of the average layer thickness being split into the catalyst layer be formed between heat transfer plate also makes this reaction raw materials catalytic gas phase oxidation come in the manufacture method of manufacturing objective reaction product, be conceived to the temperature of the thermal medium body be supplied in above-mentioned more than 2 conversion zones, thus complete the present invention.That is, main points of the present invention are as follows.
Namely, the invention provides a kind of manufacture be selected from by unsaturated hydrocarbons, carbon number be 3 and 4 unsaturated aliphatic aldehyde and carbon number be the manufacture method of more than one the reaction product in the group that forms of unrighted acid of 3 and 4, the method is the method for following (A) or (B):
(A) to supply response raw mixture in the plate-type reactor possessing the catalyst layer be formed between heat transfer plate, this reacting material mixture contain be selected from by carbon number be 3 and 4 hydrocarbon and the group that forms of the tert-butyl alcohol in reaction raw materials at least one and containing molecularity oxygen, catalytic gas phase oxidation is carried out to above-mentioned reaction raw materials, at least one reaction product in the group that the unsaturated aliphatic aldehyde that it is 3 and 4 that manufacture is selected from by unsaturated hydrocarbons and carbon number forms;
(B) for using the method possessing the plate-type reactor of the catalyst layer be formed between heat transfer plate, wherein, supply response raw mixture, this reacting material mixture contains at least one and the molecularity oxygen of the reaction raw materials in the group that unsaturated aliphatic aldehyde that to be selected from by carbon number be 3 and 4 forms, catalytic gas phase oxidation is carried out to above-mentioned reaction raw materials, at least one reaction product in the group that the unrighted acid that it is 3 and 4 that manufacture is selected from by carbon number forms;
Wherein, above-mentioned plate-type reactor is split into more than 2 different conversion zones of the average layer thickness of catalyst layer, the thermal medium body of temperature adjustment is independently carried out to above-mentioned more than 2 conversion zones supply, the heat generated by above-mentioned oxidation is carried out heat extraction across above-mentioned heat transfer plate, and independently controls the temperature in above-mentioned catalyst layer;
The temperature T (S1) being supplied to the above-mentioned thermal medium body of conversion zone S1 is higher than the temperature T (S2) of above-mentioned thermal medium body being supplied to conversion zone S2, described conversion zone S1 is closest to the entrance of above-mentioned reacting material mixture, 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 be selected from by carbon number be 3 and 4 hydrocarbon and the group that forms of the tert-butyl alcohol at least one of reaction raw materials be oxidized time, the load of above-mentioned reaction raw materials is more than 150 liter per hour [converting through standard state (temperature 0 DEG C, 101.325kPa)] relative to every 1 liter of catalyst;
The load when at least one of the reaction raw materials in the group form the above-mentioned unsaturated aliphatic aldehyde that to be selected from by carbon number be 3 and 4 is oxidized, above-mentioned reaction raw materials is more than 160 liter per hour [converting through standard state (temperature 0 DEG C, 101.325kPa)] (hereafter also referred to as " the 3rd manufacture method of reaction product ") relative to every 1 liter of catalyst.
In addition, the invention provides the 3rd manufacture method of reaction product, wherein preferably, the temperature being supplied to the specific thermal medium body of conversion zone S (j) is arbitrarily set to T (Sj), will be supplied to adjacent with above-mentioned conversion zone S (j) and the temperature being positioned at the above-mentioned thermal medium body of the conversion zone S (j+1) in the downstream of reacting material mixture stream is set to T (Sj+1) time, above-mentioned T (Sj) and above-mentioned T (Sj+1) meets T (Sj)-T (relation of 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 by the entrance of reacting material mixture towards outlet, the average layer thickness of the catalyst layer of each conversion zone increases.
In addition, the invention provides the 3rd manufacture method of reaction product, wherein preferably, to above-mentioned be selected from by carbon number be 3 and 4 hydrocarbon and the group that forms of the tert-butyl alcohol at least one of reaction raw materials be oxidized time, the load of above-mentioned reaction raw materials is 170 ~ 290 liter per hour [converting through standard state (temperature 0 DEG C, 101.325kPa)] relative to every 1 liter of catalyst.
In addition, the invention provides the 3rd manufacture method of reaction product, wherein preferably, the load when at least one of the reaction raw materials in the group formed the above-mentioned unsaturated aliphatic aldehyde that to be selected from by carbon number be 3 and 4 is oxidized, above-mentioned reaction raw materials is 180 ~ 300 liter per hour [converting through standard state (temperature 0 DEG C, 101.325kPa)] relative to every 1 liter of catalyst.
In addition, the invention provides the 3rd manufacture method of reaction product, wherein the conversion ratio of the reaction raw materials in the preferred reaction product exit at above-mentioned plate-type reactor is more than 90%.
In addition, the invention provides the 3rd manufacture method of reaction product, wherein preferably, above-mentioned reaction raw materials is propylene, and the temperature being supplied to the thermal medium body of above-mentioned more than 2 conversion zones is 320 ~ 400 DEG C; Or above-mentioned reaction raw materials is methacrylaldehyde, the temperature being supplied to the thermal medium body of above-mentioned more than 2 conversion zones is 250 ~ 320 DEG C.
In the first plate-type reactor, due to heat transfer plate in plate-type reactor surface between the measured value of distance be included in above-mentioned specific scope relative to its design load, thus can control not control reaction out of control by the temperature of thermal medium, even and if 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, the plate-type reactor be more suitable in industrial applicibility can be obtained.
In addition, in the first plate-type reactor, from the viewpoint of the measured value of the distance between the surface that can obtain heat transfer plate and the less plate-type reactor of the difference of design load, the length of the axis of above-mentioned heat transfer plate is below 5m, be preferably below 2m further effect.
In addition, in the first plate-type reactor, from the viewpoint of the measured value of the distance between the surface that can obtain heat transfer plate and the less plate-type reactor of the difference of design load, the sept had further for forming appointed interval between above-mentioned heat transfer plate has further effect.
In addition, in the first plate-type reactor, above-mentioned heat transfer plate is engaged by two steel plates and forms, these two steel plates are shaped as, multiplely with the axle of heat transfer plate, the shape that the cross sectional shape of above-mentioned heat-transfer pipe is divided into two to be connected, thus, further effect is had from the viewpoint of the measured value of the distance between the surface that can obtain heat transfer plate and the less plate-type reactor of the difference of design load.
In addition, in the first plate-type reactor, the upstream side in the ventilation direction of the unstrpped gas in the measured value of the distance between above-mentioned surface and the gap of the difference of above-mentioned design load between heat transfer plate is less, more effective from the viewpoint of the control accuracy improving reaction; In raw material reaction rate be the position of less than 70% in above-mentioned raw materials gas, that the measured value of distance between above-mentioned surface and the difference of above-mentioned design load are less than the measured value and above-mentioned design load being greater than the distance between the position of 70%, above-mentioned surface in above-mentioned reactivity difference has further effect.
In addition, in the first plate-type reactor, the total measurement (volume) in the gap between above-mentioned heat transfer plate is more than 3L, from the viewpoint of high production rate manufacture reaction product have further effect.
In addition, in the first plate-type reactor, further there is temperature measuring apparatus, this temperature measuring apparatus for measure the catalyst layer formed in the gap of packed catalyst between above-mentioned heat transfer plate 2 places more than the temperature of position, from the viewpoint of improve reaction control accuracy have further effect.
In addition, in the first manufacture method of reaction product, the reaction of the raw material in the presence of a catalyst in unstrpped gas is exothermic reaction, from the viewpoint of significantly obtaining the more effective of 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 more entering one deck.
In addition, in the preparation method of the first plate-type reactor, use in above-mentioned heat transfer plate the error of the design load of the shaping relative to steel plate be ± 0.5mm within shaping steel plate, from the viewpoint of reduce measured value and above-mentioned design load difference have further effect.
In addition, in the preparation method of the first plate-type reactor, distance across between the surface for forming relative heat transfer plate between heat transfer plate becomes the sept at the interval of design load to configure the heat transfer plate before joint, from the viewpoint of reduce measured value and above-mentioned design load difference have further effect.
In the second plate-type reactor, owing to having aforementioned barriers, the catalyst of the amount corresponding to the capacity of each section formed by dividing plate can be filled; By making the occupied state of catalyst in each section be constant, can catalyst filling equably in the whole gaps between the adjacent heat transfer in plate-type reactor.Thus, for plate-type reactor of the present invention, compared with existing plate-type reactor, can evenly and easily by the gap between packed catalyst to adjacent heat transfer.
In addition, in the second plate-type reactor, above-mentioned 2 identical with upper curtate volume separately, consider there is further effect from being easy to make the constant aspect of the occupied state of catalyst each section.
In addition, in the second plate-type reactor, above-mentioned 2 with the respective volume of upper curtate for 1 ~ 100L, consider there is further effect from the aspect being easy to the filling operation carrying out catalyst each section.
In addition, in the second plate-type reactor, above-mentioned 2 with the respective volume of upper curtate for 2 ~ 25L, consider there is further effect from the aspect being easy to the filling operation carrying out catalyst each section.
In addition, in the second plate-type reactor, there is above-mentioned breather plug further, from being carried out taking out with section unit by the catalyst in the gap be filled between adjacent heat transfer, by catalyst evenly and the gap be easily filled between adjacent heat transfer and the aspect of the occupied state of catalyst easily the above-mentioned gap of adjustment considers there is further effect.
In addition, in the second plate-type reactor, there is above-mentioned first fastener, above-mentioned vent board, above-mentioned skirt section and above-mentioned second fastener, from the viewpoint of breather plug with sufficient intensity be fixed on each section end and be easy to the charge and discharge operations carrying out breather plug simultaneously have further effect.
In addition, in the second plate-type reactor, above-mentioned 2 are spaced apart 0.1 ~ 1m with upper spacer, consider there is further effect from the aspect being easy to the packed catalyst operation carried out each section.
In recent years, chemicals is produced in a large number mainly with large-scale equipment, and the reactor be arranged in manufacturing equipment is maximization, the catalytic amount that inserts also is a large amount of, in large-scale reactor evenly, efficiently catalyst filling be very important.Particularly when producing or absorption reaction heat and temperature caused by reaction heat rise or decline reaction speed or reaction achievement, further reaction influential to the degradation of catalyst, make the reaction raw materials such as gas and liquid and catalyst uniform contact, this is significant problem in the reactor that design is more good.
In the second manufacture method of reaction product, above-mentioned raw materials is ethene; Be selected from by carbon number be 3 and 4 hydrocarbon and the group that forms of the tert-butyl alcohol at least one or at least one in the group that forms of unsaturated aliphatic aldehyde that to be selected from by carbon number be 3 and 4; Carbon number is the hydrocarbon of more than 4; Dimethylbenzene and/or naphthalene; Alkene; Carbonyls; Cumene hydroperoxide; Butylene; Or ethylbenzene, the above-mentioned reaction product obtained is ethylene oxide; Carbon number be 3 and 4 unsaturated aliphatic aldehyde and/or carbon number be the unrighted acid of 3 and 4; Maleic acid; Phthalic acid; Alkane; Alcohol; Acetone and phenol; Butadiene; Or styrene; In this manufacture method, owing to using above-mentioned plate-type reactor, therefore the catalyst treatment of above-mentioned reaction raw materials through between uniform filling to heat transfer plate, so can improve heat extraction or the heating means of reaction heat in such haptoreaction, considers there is further effect from the side.
In addition, in the 3rd manufacture method of reaction product, supply response raw material in the plate-type reactor being filled with catalyst, makes this reaction raw materials react to manufacture product; In this manufacture method, when improving the processing load amount of reaction raw materials of unit catalyst, the increase of the pressure loss of the reacting fluid by catalyst can be prevented, and by carrying out suitable control to prevent heat spot to the heat generated by reaction, the yield of goal response product can be improved while preventing catalyst from damaging.
Accompanying drawing explanation
Fig. 1 is the figure of the formation of the plate-type reactor schematically shown in one embodiment of the present invention.
Fig. 2 is sectional view when cutting off the plate-type reactor of Fig. 1 along A-A ' line.
Fig. 3 is sectional view when cutting off the plate-type reactor of Fig. 1 along B-B ' line.
Fig. 4 is the figure of an example of the outward appearance of the plate-type reactor of display Fig. 1.
Fig. 5 is the figure of the size of display heat-transfer pipe 1.
Fig. 6 is the figure of an example of display thermal medium mixing arrangement.
Fig. 7 is the figure of an example of display dividing plate 7.
Fig. 8 is the figure of an example of display breather plug 8.
Fig. 9 is the figure of an example of the state that arranges of display breather plug 8.
Figure 10 is the figure of an example of displays temperature determinator 9.
Figure 11 is the figure of the example being presented at the catalyst layer formed in the gap between heat transfer plate 2.
Figure 12 is the figure of other form schematically showing heat transfer plate.
Figure 13 is the figure of the formation schematically showing the second embodiment in plate-type reactor of the present invention.
Figure 14 is the figure in the cross section shown when cutting off the plate-type reactor of Figure 13 along A-A ' line.
Figure 15 is the figure in the cross section shown when cutting off the plate-type reactor of Figure 13 along B-B ' line.
Figure 16 is display adjacent heat transfer 2 and the figure being located at dividing plate 7 therebetween.
Figure 17 is the figure of an example of display dividing plate 7.
Figure 18 is the figure of other example of display dividing plate 7.
Figure 19 is the figure of other example of display dividing plate 7.
Figure 20 is the figure of other example of display dividing plate 7.
Figure 21 is the figure of other example of display dividing plate 7.
Figure 22 is the figure of other example of display dividing plate 7.
Figure 23 is the figure of the formation schematically showing the 3rd embodiment in plate-type reactor of the present invention.
Figure 24 is the figure in the cross section illustrated when cutting off the plate-type reactor of Figure 23 along A-A ' line.
Figure 25 is the figure in the cross section illustrated when cutting off the plate-type reactor of Figure 23 along B-B ' line.
Figure 26 is the figure that dividing plate 7 is shown.
Figure 27 is the figure that adjacent heat transfer 2 and the dividing plate 7 be located at therebetween and breather plug 8 are shown.
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 of the free construct for handling that breather plug 8 and dividing plate 7 are shown.
Figure 31 is the figure of an example of the instrument of the dismounting illustrated for breather plug 8.
Figure 32 is the figure of other free construct for handling that breather plug 8 and dividing plate 7 are shown.
Figure 33 is the figure of other example that breather plug used in the present invention is shown.
Figure 34 is the figure of other example that breather plug used in the present invention is shown.
Figure 35 is the figure of other example that breather plug used in the present invention is shown.
Figure 36 is the figure of other example that breather plug used in the present invention is shown.
Figure 37 is the figure of other example that breather plug used in the present invention is shown.
Figure 38 is the figure of other example that breather plug used in the present invention is shown.
Figure 39 illustrates that the figure of formation is fixed in other example of breather plug used in the present invention and its handling.
Figure 40 illustrates that the figure of formation is fixed in other example of breather plug used in the present invention and its handling.
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 retention bar
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 ン ホ ー Le)
20 windows
21 vent boards
22 first skirt sections
23 second skirt sections
24 locking windows
25,50,51 engagement pawl
26 supports
27 temperature measuring portions
28 spacer rods
29 flanges
30 connectors
31 cable (ケ ー 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 P a pair heat transfer plate
L wave period
The height of H ripple
Y represents the arrow of thermal medium flow direction
X interval
Detailed description of the invention
< first plate-type reactor >
First plate-type reactor having reaction vessel for making gaseous feed react, being disposed side by side on more than 2 heat transfer plates in above-mentioned reaction vessel and the thermal medium feedway for the thermal medium to the desired temperature of above-mentioned heat transfer plate supply.
In above-mentioned reaction vessel, supply gaseous feed (unstrpped gas) can be used, discharge and generate gas and hold the container of more than 2 heat transfer plates side by side.Due to the reaction in the atmosphere that plate-type reactor is generally used under an increased pressure, thus above-mentioned reaction vessel is preferably the resistance to pressure container of pressure in tolerance 3,000kPa (kPa).As such reaction vessel, such as can enumerate following container etc., this container has combination and has the shell of cylindrical portion or its part (shell), utilize plate member split to hold the shell of more than 2 heat transfer plates to inside and surrounded to hold the inside of housing shape of more than 2 heat transfer plates by the parts forming plane inner face.
Above-mentioned heat transfer plate comprises and carries out with the periphery of cross sectional shape or ora terminalis more than 2 heat-transfer pipes linking in the vertical direction.Like this, heat transfer plate is the plate body comprising more than 2 heat-transfer pipes arranged side by side.In the heat transfer plates, heat-transfer pipe can directly connect, and also indirectly can be connected by the parts that plate or hinge etc. are suitable.From the viewpoint of obtaining heat transfer plate with low cost, preferred heat transfer plate forms by being engaged by two steel plates, and these two steel plates are configured as the shape multiple connected shape be directly or indirectly divided into two by the cross sectional shape of heat-transfer pipe separately.
The interval of above-mentioned heat transfer plate sets according to design load, can be at equal intervals, also can be the different interval of more than two kinds.Such as when the interior shape of reaction vessel is rectangle, the mode that heat transfer plate can be parallel to each other according to the axle of heat transfer plate between heat transfer plate, the axle of heat-transfer pipe is parallel to each other between heat transfer plate is arranged.In addition when the inside of such as reaction vessel is cylindric, heat transfer plate can be arranged in a manner described, can be also the radial direction of the cross section of reaction vessel according to the axle of heat transfer plate, the axle of heat-transfer pipe is parallel to each other between heat transfer plate mode (namely radially) arranges.
There is no particular restriction for the number of the heat transfer plate held in above-mentioned reaction vessel, and the catalytic amount in practicality needed for reaction is determined, is generally tens of to hundreds of.In addition, for the number of the heat transfer plate held in above-mentioned reaction vessel, consider from the large-duty aspect the industrial production of realization response product, the total capacity in the gap between heat transfer plate is preferably made to be the number of more than 3L (liter), be more preferably and make above-mentioned total capacity be the number of more than 100L, more preferably make above-mentioned total capacity be the number of more than 250L.Sept is inserted in gap when between heat transfer plate, preferably by sept and heat transfer plate the volume of a section that surrounds be more than 1L, be more preferably more than 10L.
For the axle base of the above-mentioned heat transfer plate be contained in reaction vessel, consider in control reaction temperature abundant gas phase haptoreaction, 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 cutting off heat transfer plate along the gas ventilation direction in above-mentioned gap, when heat-transfer pipes whole in the heat transfer plates connects in a straight line, the axle of heat transfer plate refers to this straight line, and when the connecting portion of whole heat-transfer pipe is out-of-line, the axle of heat transfer plate refers to the straight line of the mid point between two parallel lines by clipping whole connecting portion.
For the axle base of above-mentioned heat transfer plate, from effectively removing along with the heat of reacting, preventing the aspect of the deterioration of the catalyst caused by the heat spot (exothermic reaction) of catalyst layer to consider, in addition from the viewpoint of whole for catalyst layer layer temperature is everywhere controlled obtain at optimum range high reactivity and high response can, preferably count 10 ~ 50mm 1.1 ~ 5 times of half value sum of heat-transfer pipe width (in the adjacent heat transfer) with mean value, be more preferably 10 ~ 40mm, more preferably 20 ~ 35mm.
The axle base of above-mentioned heat transfer plate is on the reactivity of the diameter (being usually preferably 1 ~ 10mm in industrial catalyst) of catalyst, catalyst, also have impact to the resistance to elevated temperatures of catalyst further.For the heat extraction of reaction heat, the less reaction of axle base of heat transfer plate more easily controls, if but be not the axle base of the heat transfer plate of more than 5 ~ 10 times of catalyst diameter, then bridge joint (Block リ ッ ジ Application グ) can occur when catalyst filling, and packed density likely can reduce.
Above-mentioned heat transfer plate can arrange according to the mode that the flange on the surface of heat transfer plate is opposite to one another in above-mentioned reaction vessel, also can arrange according to the mode that the surfaces lips of side's heat transfer plate is relative with the recessed edge in the surface of the opposing party's heat transfer plate.
For above-mentioned heat-transfer pipe, when above-mentioned heat transfer plate is contained in reaction vessel, the axle of heat-transfer pipe is configured in the direction relative to the ventilation direction crosscut in reaction vessel usually.Now, for the angle between the ventilation direction in the axle of heat-transfer pipe and reaction vessel, as long as the axle of heat-transfer pipe, relative to the ventilation direction crosscut of gas, is not particularly limited in reaction vessel.For heat-transfer pipe, from the viewpoint of to be controlled the reaction of raw material by the temperature of thermal medium in adjustment heat-transfer pipe, more preferably the axle of the heat-transfer pipe flow direction of thermal medium that is orthogonal relative to the ventilation direction in reaction vessel, that namely flow in heat-transfer pipe is orthogonal relative to the ventilation direction in reaction vessel.
Above-mentioned heat-transfer pipe preferably makes the material of the conductivity of heat that heat exchange occurs between the thermal medium in heat-transfer pipe and the catalyst layer being external to heat-transfer pipe be formed by having.As such material, such as stainless steel and carbon steel, Hastelloy, titanium, aluminium, engineering plastics and copper can be enumerated.Preferred use stainless steel.In stainless steel, preferably 304,304L, 316 and 316L.The cross sectional shape of heat-transfer pipe can be circular; Can be that ellipse, elliposoidal etc. intend circle; Can be leaf for what circular arc symmetry was formed by connecting; Can be the polygons such as rectangle; Also can be by these multiple shapes combined.Periphery in the cross sectional shape of heat-transfer pipe refers to the periphery in circle, the ora terminalis in the cross sectional shape of heat-transfer pipe refer to intend in major axis ora terminalis in circle or polygon edge.
In each heat transfer plate, for the diameter of the above-mentioned heat-transfer pipe of heat transfer plate axis, from bending resistance (anti-crawl agentdefiection) rigidity fully guaranteeing the direction that (1) is orthogonal with the axle of heat transfer plate and both axles of heat-transfer pipe, (2) formability of heat-transfer pipe shape and forming accuracy, (3) aspect removing the necessary heat transfer area of reaction heat is considered, and from obtaining the flow distribution of reacting gas and the heat transfer coefficient of catalyst layer of (4) appropriateness, (5) the thermal medium flow velocity of the appropriateness in heat-transfer pipe and the aspect of heat transfer coefficient are considered, be preferably 10 ~ 100mm, be more preferably 15 ~ 70mm, more preferably 20 ~ 50mm.
In addition, in each heat transfer plate, for the radius of the above-mentioned heat-transfer pipe on the direction orthogonal with the axle of heat transfer plate, 1.5 ~ 25mm is thought of as from the aspect of the reaction temperature fully controlled gas phase haptoreaction.For the radius of above-mentioned heat-transfer pipe, control distance between adjacent heat transfer accordingly from the reaction heat produced between (1) with this heat transfer plate, adjust the angle of catalyst layer temperature; Fully guarantee the necessary heat transfer area of heat extraction of (2) reaction heat and the formability of (3) heat-transfer pipe shape and the angle of forming accuracy; From obtain appropriateness (4) reacting gas velocity flow profile disorder and the heat transfer coefficient of catalyst layer, the pressure loss of (5) reacting gas and (6) heat-transfer pipe in the flow velocity of thermal medium and the angle of heat transfer coefficient consider, preferably 1.5 ~ 25mm, be more preferably 3 ~ 20mm, more preferably 5 ~ 15mm.
In plate-type reactor, the distance between heat transfer plate adjusts usually for the purpose of the temperature of catalyst layer.In the axis and direction orthogonal to the axis of above-mentioned heat transfer plate, the particle diameter of the Distance geometry catalyst of heat-transfer pipe radius separately also and between heat transfer plate is related, by make described radius be above-mentioned record scope in can reach above-mentioned purpose.
It should be noted that, the shape and size in more than 2 heat-transfer pipe cross sections separately in a heat transfer plate can necessarily also can be different.
In addition, heat-transfer pipe length is axially not specially limited, and is generally 0.5 ~ 20m.From a large amount of aspect producing reaction product, the length of heat-transfer pipe axis is preferably 3 ~ 15m, is more preferably 6 ~ 10m.
Be out of shape from the viewpoint of preventing the flexure etc. of the heat transfer plate be contained in reaction vessel, be preferably below 5m in the length of the axis (that is, the closure of the heat-transfer pipe on the cross section of the heat-transfer pipe orthogonal with the axle of heat-transfer pipe) of heat transfer plate, be more preferably 0.5 ~ 2m, more preferably 0.5 ~ 1.5m.
When making heat transfer plate the plate width specification of steel plate used and the easiness of acquisition for practicality and the making of the heat transfer plate of low cost is very important, usually, the size of the steel plate that can obtain also be in the world 1.5 ~ 2m or its below.Therefore, when plate width exceedes above-mentioned practical dimensions, also the steel plate of more than 2 can be engaged into enforcement use, but the formability at junction surface for steel plate, its forming accuracy likely reduces.
For the design load of the distance between the surface realizing heat transfer plate, error caused during steel formability is very important.Error caused during steel formability has the error of heat-transfer pipe axis and the error of heat-transfer pipe closure, and they are all very important.When particularly changing the distance between the surface between heat transfer plate on the flow direction (being generally the closure of heat-transfer pipe) of reacting gas, the shape form accuracy of the heat-transfer pipe on the flow direction of reacting gas is particular importance.Suppress below desired value from the viewpoint of by these errors, the length of heat transfer plate axis is preferably below 2m.
The design load of the distance between the surface of relative above-mentioned heat transfer plate is 5 ~ 50mm.Distance between the surface of so-called heat transfer plate herein refers to the gap between relative heat transfer plate, the distance between the surface of the heat transfer plate on the direction orthogonal with apart from equidistant, the face formed by the axle of above-mentioned heat transfer plate.Or the distance between the surface of so-called heat transfer plate refers to, when observing above-mentioned heat transfer plate from above-mentioned gap, in the cross section of the heat transfer plate when cutting off heat transfer plate along the gas ventilation direction in above-mentioned gap, the distance between the surface of the heat transfer plate on the direction orthogonal with the equidistant line of axle apart from above-mentioned heat transfer plate.When heat-transfer pipe is connected with thermal medium feedway, in order to prevent thermal medium in reaction vessel spill and gas by reaction vessel spilling to heat-transfer pipe or thermal medium feedway, usually heat-transfer pipe is engaged with thermal medium feedway by welding.Thus, in reaction vessel, heat transfer plate is usually to be irreversibly fixed.Therefore, the configuration of the heat transfer plate in 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 controlling and reaction achievement.The condition of reaction controlling such as can be determined based on the higher limit of the absolute value of the peak temperature of reaction time catalizer layer.Reaction achievement such as can consider that the conversion ratio of raw material and the selection rate of product are mainly determined based on the productive rate of product.For above-mentioned design load, can consider the extra factor such as temperature of the kind of catalyst, the composition of unstrpped gas and flow and thermal medium, the form of the distance between the thickness of catalyst layer during to meet the condition of reaction controlling and to meet the condition of reaction achievement, the surface of heat transfer plate is tried to achieve.In addition, the peak temperature of catalyst layer in exothermic reaction be catalyst layer maximum temperature, be the minimum temperature of catalyst layer in the endothermic reaction.
Above-mentioned design load can be tried to achieve by such as under type: based on the calculating of computer simulation; Based on the experiment of testing machine, such as, have and only have the plate-type reactor of the simple formations such as a pair heat transfer plate or the total saturation of catalyst to be the testing machines such as the small-sized plate-type reactor of about 3L; Or based on the experiment of pipe reaction testing machine, this pipe reaction testing machine has a reaction tube being filled with catalyst and makes thermal medium at the chuck of reaction tube surrounding loop.Computer simulation such as can use the softwares such as the gPROMS of STAR-CD, PSE society of CFX, CD adapco society of ANSYS Co., Ltd. to carry out.
For above-mentioned design load, from the aspect of productivity ratio (space time yield) of the reaction product of the precise hard_drawn tuhes of reaction and reaction achievement (reaction yield or selection rate), unit catalyst amount, this design load is preferably 5 ~ 50mm, is more preferably 7 ~ 30mm, more preferably 10 ~ 25mm.In order to reach the high production rate of catalyst, the distance between the surface of heat transfer plate is little, be easy to carry out temperature control, can carry out the precise hard_drawn tuhes that reacts, but the distance between the surface of heat transfer plate is also subject to the restriction of the particle diameter of inserted catalyst.In industrial catalyst, the many employing 1 ~ 10mm of particle diameter of catalyst, also from the aspect of these conditions, above-mentioned design load also preferably can be determined in above-mentioned scope.
The measured value of the distance between the surface of relative above-mentioned heat transfer plate and the difference (measured value-design load) of design load are-0.6 ~+2.0mm."-" represents that above-mentioned measured value is less than above-mentioned design load herein, and "+" represents that above-mentioned measured value is greater than above-mentioned design load.
As long as the distance between the surface of above-mentioned heat transfer plate is in the scope of 5 ~ 50mm, can be the surface of relative heat transfer plate any position between distance.Such as, when the heat-transfer pipe ventilation direction of the unstrpped gas among the heat-transfer pipe comprised at heat transfer plate, in reaction vessel being positioned at side, most upstream is as heat-transfer pipe A, the distance between the surface of heat transfer plate can be the distance between flange that in relative a pair heat transfer plate, heat-transfer pipe A produces; Also can be in relative a pair heat transfer plate heat-transfer pipe A and and the adjacent heat-transfer pipe in its downstream between the recessed intermarginal distance that produces of connecting portion; It can also be the distance between recessed edge and flange, this recessed edge be heat-transfer pipe A in the heat transfer plate of a side or the opposing party in relative a pair heat transfer plate and and the adjacent heat-transfer pipe in its downstream between the recessed edge that produces of connecting portion, this flange is the flange produced with the heat-transfer pipe A in the heat transfer plate of the opposing party or a side.
Distance between the surface of above-mentioned heat transfer plate such as can measure by inserting the rod with the design load of the distance between this surface with identical thickness.In addition, distance between the surface of above-mentioned heat transfer plate such as can be tried to achieve as follows: insert components of assays in above-mentioned gap, this components of assays has and is inserted into insertion pole member in above-mentioned gap and measures pole member, and this mensuration pole member has the length of above-mentioned design load in the front end of inserting pole member and the axle orthogonal configuration inserting pole member.The angle of the axle of the insertion pole member measured when the end of pole member contacts with the surface of the heat transfer plate in above-mentioned gap or the anglec of rotation are measured, thus by this angle obtain with measure pole member contact heat transfer plate partly surface between distance.
If the difference of above-mentioned measured value and above-mentioned design load is greater than+2.0mm, then likely fully can not control the reduction reacting, suppress runaway reaction, prevent the deterioration of catalyst and prevent reaction yield.In addition, if the difference deficiency-0.6mm of above-mentioned measured value and above-mentioned design load, then catalyst can produce obstacle to the supply in the gap between heat transfer plate, or namely allow to the supply carrying out catalyst with no obstacle, the packed density of the catalyst layer formed also can reduce, and has catalytic amount to be not enough to reach the situation of desired reactivity.From the aspect of carrying out more accurate reaction controlling, the difference of above-mentioned measured value and above-mentioned design load is preferably-0.5 ~+1.5mm, is more preferably-0.5 ~+1.0mm, more preferably-0.3 ~+1.0mm.
In addition, although wish that the difference of above-mentioned measured value and above-mentioned design load is in the scope of-0.6 ~+2.0mm in whole plate-type reactor most, but from the viewpoint of not only preventing runaway reaction but also remain large-duty, preferably more than 50% among whole measured value and the difference of above-mentioned design load are included in the scope of-0.6 ~+2.0mm, more preferably more than 70% among whole measured value and the difference of above-mentioned design load are included in the scope of-0.6 ~+2.0mm, preferably more than 80% be included in the scope of-0.6 ~+2.0mm with the difference of above-mentioned design load further, further preferably more than 90% be included in the scope of-0.6 ~+2.0mm with the difference of above-mentioned design load.
The measuring point of above-mentioned measured value is axially preferably 2 ~ 30 heat transfer plate, is more preferably 5 ~ 25, more preferably 10 ~ 20.In addition, above-mentioned measured value measuring point heat transfer plate heat-transfer pipe be axially preferably 2 ~ 50, be more preferably 5 ~ 30, more preferably 10 ~ 20.
As described later, in order to control the interval of adjacent heat transfer, insert sept (dividing plate) between heat transfer plate, sept has the effect at the interval of adjustment heat transfer plate in this case, thus in this case, the middle position of above-mentioned measured value between sept measures 2 positions.The interval that arranges when arranging more than 2 septs is generally 50cm ~ 1m, but by using the heat transfer plate that rigidity is high, try every possible means to arrange the side plate itself that is engaged with each other by heat transfer plate or manage to utilize welding method, as long as the distance thus between energy Heat Transfer Control plate, also can be set to more than 1m by the distance between sept.
For the difference of above-mentioned measured value and above-mentioned design load, such as it can be made in the scope of-0.6 ~+2.0mm by carrying out following method, described method is: when the joint by two shaping steel plates forms heat transfer plate, the method for (such as error is ± below 0.5mm) that choice for use is enough little relative to the error of the design load of steel formability, shaping steel plate that precision is high; And the shaping steel plate that selection precision is inadequate, carry out the method revising to improve precision to use.About the error of the design load relative to steel formability, such as laser type extensometer can be set on the two sides of shaping steel plate, by mobile extensometer or steel plate, the displacement on shaping steel plate two sides can be measured thus, obtain the shape of shaping steel plate, its forming accuracy and the error relative to above-mentioned design load.
And then, the heat-transfer pipe being below 10m by the length axially of heat-transfer pipe is used for above-mentioned heat-transfer pipe, effective from the viewpoint of what prevent the flexure of heat-transfer pipe or heat transfer plate, from the viewpoint of make the difference of above-mentioned measured value and above-mentioned design load be-0.6 ~+2.0mm be preferred.
The difference of above-mentioned measured value and above-mentioned design load can be single value, but according to prediction reactivity when being applied to gas phase haptoreaction, can be axially the different values of more than 2 at heat transfer plate.Such as, in gas phase haptoreaction, in gap particularly between the heat transfer plate carrying out the reaction that reaction is fierce, raw material reaction rate is little, by making the above-mentioned difference being less than the export department in unstrpped gas at the above-mentioned measured value of the inlet portion of unstrpped gas and the difference of above-mentioned design load, namely by making the upstream side in the ventilation direction in the gap of the difference of above-mentioned measured value and above-mentioned design load between heat transfer plate less, be preferred from the viewpoint of what suppress runaway reaction.
From the viewpoint of such, preferably making in raw material reaction rate is that the difference of the above-mentioned measured value of the position of less than 70% and above-mentioned design load is less, more preferably making in raw material reaction rate is that the difference of the above-mentioned measured value of the position of less than 60% and above-mentioned design load is less, and preferably making further in raw material reaction rate is that the difference of the above-mentioned measured value of the position of less than 50% and above-mentioned design load is less.In addition, from above-mentioned aspect, the difference of the above-mentioned measured value on above-mentioned position and above-mentioned design load with the above-mentioned measured value on other position compared with the difference of above-mentioned design load, preferably with little more than the 0.2mm of absolute value, more preferably with little more than the 0.5mm of absolute value.
In gap between above-mentioned heat transfer plate, be that the position of predetermined value is determined according to the carrying out of distance, the kind of catalyst and the composition of unstrpped gas between the surface of the cross sectional shape of heat-transfer pipe and size, the temperature flowing through the thermal medium of heat-transfer pipe and flow thereof, heat transfer plate and its flow etc. and reaction and relevant all conditions of conduct heat in the axially raw material reaction rate of above-mentioned heat transfer plate, such as by the experiment based on above-mentioned testing machine or can determine based on the calculating that above computer 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 for the device of the thermal medium to the desired temperature of heat-transfer pipe supply.For above-mentioned thermal medium feedway, the common device for supplying thermal medium in plate-type reactor to above-mentioned heat-transfer pipe can be utilized.Thermal medium feedway can be more than 2 heat-transfer pipes all supply device from thermal medium to same direction, also can be that a part for more than 2 heat-transfer pipes supplies thermal medium to a direction, the other parts of more than 2 heat-transfer pipes supply the device of thermal medium round about.
In addition, from the viewpoint of axially forming more than 2 conversion zones at catalyst layer along heat transfer plate, preferred its of thermal medium feedway has the thermal medium circular chamber of more than 2 that the direction along crosscut heat transfer plate axis is split to form.In addition, thermal medium feedway makes thermal medium inside and outside reaction vessel, carry out the device circulated preferably by above-mentioned heat-transfer pipe.
Further, thermal medium feedway has the device of the temperature for adjusting the thermal medium being supplied to heat-transfer pipe.As such device, such as, can enumerate: be arranged on the thermal medium mixing arrangement of the heat exchanger in the circulation stream of thermal medium and the thermal medium for mixing different temperatures in the thermal medium of above-mentioned room in thermal medium feedway, thermal medium temperature measuring apparatus, for regulating the device of the flow of thermal medium.In above-mentioned thermal medium mixing arrangement, such as can use distributing pipe, be located at the logical liquid plate in thermal medium feedway and be commonly called the silent oscillation blender of static mixer, outstanding in this distributing pipe thermotropism medium supply apparatus, and thermal medium dispersion can be supplied in thermal medium feedway.
As above-mentioned distributing pipe, the length direction such as can enumerated along distributing pipe has the distributing pipe of such more than 2 fluid-through ports of slit or hole at tube wall and has the distributing pipe of the arm with fluid-through port further.Above-mentioned distributing pipe preferably extends setting in the direction orthogonal relative to the flow direction of thermal medium in thermal medium feedway, the distributing pipe with arm has supervisor and arm, from the aspect raising the efficiency and suppress the pressure loss in the dispersion of the thermal medium of different temperatures, preferably supervisor and the arm one inherent direction orthogonal relative to the flow direction of thermal medium of thermal medium feedway that coexist extends and arranges and arrange according to the mode extending direction mutually orthogonal of supervisor and arm.
In the first plate-type reactor, also can have other constitutive requirements other than the above further.As other such constitutive requirements, such as, can enumerate sept, breather plug, temperature measuring apparatus and plate clamping part.
Above-mentioned sept (dividing plate) is the parts for forming appointed interval between above-mentioned heat transfer plate.Preferred above-mentioned sept abuts with the surface of heat transfer plate, and has sufficient rigidity in the interval keeping heat transfer plate.In addition, when sept is formed by steel, from the viewpoint of the amount of the steel cut down required for plate-type reactor, preferred above-mentioned sept is the parts abutted intermittently with the surface of heat transfer plate in the axis of heat transfer plate.In addition, from the viewpoint of preventing the flexure etc. of heat transfer plate in reaction vessel to be out of shape, preferred above-mentioned sept is the parts abutted continuously with the surface of heat transfer plate in the axis of heat transfer plate.Further, from the filling aspect of catalyst, from the viewpoint of the gap between above-mentioned heat transfer plate can be divided into specified vol section, by catalyst easily and be accurately filled into the gap between heat transfer plate, preferred above-mentioned sept is do not allow in the axis of heat-transfer pipe the parts that catalyst passes through.From the viewpoint of the distortion preventing heat transfer plate in reaction vessel, preferred interval thing configures more than axial arrangement 10 place of heat-transfer pipe or with the interval of 100 ~ 1,000mm.As above-mentioned sept, such as, can enumerate the dividing plate in the parts of the various forms such as rod, plate, block and aftermentioned second plate-type reactor.
Above-mentioned breather plug has aeration, and be as lower component: for detachably inaccessible heat transfer plate gap or detachably inaccessible there is sept further when above-mentioned section, the end of the axis of heat transfer plate, not allow the parts that catalyst passes through.As such breather plug, such as can enumerate the parts with vent board and latch for printed circuit, the above-mentioned gap of vent board obturation between the heat transfer plate axially of heat transfer plate or the end of above-mentioned section, above-mentioned latch for printed circuit is located on this vent board, and detachably engages with above-mentioned heat transfer plate or above-mentioned sept.From the viewpoint of the gap-fill catalyst easily and accurately between heat transfer plate, preferred above-mentioned breather plug is the parts of the end being detachably configured in above-mentioned section.Above-mentioned breather plug can use the breather plug in aftermentioned second plate-type reactor.
Said temperature determinator is the device of the temperature of the catalyst layer measuring the gap be formed between above-mentioned heat transfer plate.As such temperature measuring apparatus, the device comprising the temperature measuring portion that there is flexual support and supported by this support can be enumerated.As above-mentioned support, can use and there is flexual rope, band, chain, pipe.In addition, as said temperature determination part, such as platinum temperature detecting resistance body, thermistor, thermocouple and optical-fiber type temperature measuring device can be enumerated.
From the viewpoint of the temperature holding catalyst layer, in each reaction vessel, said temperature determinator arranges number preferably 2 ~ 20.In addition, the thickness (wide) of preferred support is 0.5 ~ 5mm.Further, consider from the aspect making the temperature measuring of catalyst layer be reflected in the control of reaction, preferably 1 ~ 30 temperature measuring portion is set in a support, when catalyst layer is formed with more than 2 conversion zones, preferably 1 ~ 10 temperature measuring portion is set relative to a conversion zone.For said temperature determinator, in gap between above-mentioned heat transfer plate, be set as linearity by being opened by above-mentioned support on the distance equidistant position of adjacent heat transfer, open the state of establishing at above-mentioned support under by packed catalyst in above-mentioned gap, suitably can be configured in above-mentioned gap thus.From the object of the impact of the Temperature Distribution exception on partial reaction exception and catalyst layer detected caused by the form error of the distortion of heat transfer plate, heat-transfer pipe, it is more than 2 places that temperature measuring position needs in a catalyst layer.From the angle of the easiness of reaction controlling, preferable temperature locates as many places.
Above-mentioned plate clamping part is at least connected to the heat transfer plate at the two ends on above-mentioned heat transfer plate direction side by side to shield the ventilation of unstrpped gas along the axis of heat-transfer pipe, with the parts at heat transfer plate above-mentioned more than 2 heat transfer plates of direction clamping side by side.Plate clamping part can be arranged in reaction vessel, also can form a pair relative wall of reaction vessel.The aspect of the formation in the delay portion of the gas from the wall preventing 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 more than 2 heat transfer plates direction side by side, with heat-transfer pipe extend a pair grip block and through such grip block the retention bar kept that the whole heat-transfer pipes on direction abut against.
Further, from to and the interval of clamped heat transfer plate carry out inching aspect, from the aspect of the scaffold (sufficient Games) when easily arranging the inspection of packed catalyst or plate-type reactor inside and from the viewpoint of the plate-type reactor can converted as other condition, more preferably retention bar such as at least have in leading section the rod that can twist the screw buckling nut such, can at predetermined intervals by parts that grip block connects on relative direction.
In the first plate-type reactor, under this plate-type reactor is used for the catalytic situation of gas phase, the gap-fill catalyst between above-mentioned heat transfer plate.Above-mentioned catalyst is selected according to the catalytic raw material of gas phase and reaction product.Above-mentioned catalyst can be used in gas phase haptoreaction the common granular catalyst in the gap be filled between pipe or heat transfer plate.Catalyst can be that one also can for two or more.As such catalyst, can enumerate such as particle diameter (most major diameter) is the catalyst of 1 ~ 20mm.The particle diameter of the catalyst used is more preferably 1 ~ 10mm.In addition, as the shape of catalyst, known shape can be used, such as, can enumerate spherical, cylindric, Raschig ring shape, saddle.
First manufacture method > of < reaction product
First plate-type reactor has heat-exchange capacity, may be used for the exothermic reaction or the endothermic reaction that need hot-swap feature in the reactor that use in the gas phase haptoreaction of unstrpped gas and solid catalyst.Namely, first plate-type reactor may be used for the first manufacture method of following reaction product: the method comprises and in above-mentioned reaction vessel, supplies gaseous feed and make it by the operation of above-mentioned catalyst layer and the operation supplying the thermal medium of predetermined temperature in more than 2 heat-transfer pipes forming above-mentioned heat transfer plate, and under the existence of above-mentioned catalyst, makes unstrpped gas react generate vapor reaction product.Such manufacture method can be carried out in the same manner as using the gas phase haptoreaction of known plate-type reactor, or can carry out under identical condition with using the gas phase haptoreaction of known multi-tubular reactor.
As the above-mentioned gas phase haptoreaction being attended by exothermic reaction, can enumerate such as: generate methacrylaldehyde and/or acrylic acid reaction by propane, propylene and oxygen; The reaction of MAL and/or methacrylic acid is generated by isobutene and oxygen; The reaction of ethylene oxide is generated by ethene and oxygen; By carbon number be 3 hydrocarbon and oxygen Formed atomicity be the unsaturated aliphatic aldehyde of 3 and/or the reaction of unrighted acid; By carbon number be 4 hydrocarbon and/or the tert-butyl alcohol and oxygen Formed atomicity be the unsaturated aliphatic aldehyde of 4 and/or the reaction of unrighted acid; By carbon number be 3 or 4 unsaturated aliphatic aldehyde and oxygen Formed atomicity be the reaction of the unrighted acid of 3 or 4; By the carbon number such as normal butane, benzene be more than 4 hydrocarbon and oxygen generate the reaction of maleic acid; The reaction of phthalic acid is generated by dimethylbenzene and/or naphthalene and oxygen; The reaction of butadiene is generated by the oxidative dehydrogenation of butylene.
As the above-mentioned gas phase haptoreaction being attended by the endothermic reaction, such as, can enumerate and generate cinnamic reaction by the dehydrogenation of ethylbenzene.
First manufacture method of reaction product can suitably for the manufacture of MAL and/or methacrylic acid, methacrylaldehyde and/or acrylic acid, maleic acid, phthalic acid, ethylene oxide or butadiene.
Such as, for the first manufacture method manufacturing (methyl) methacrylaldehyde (methacrylaldehyde or MAL) and/or (methyl) acrylic acid reaction product, except using except the first plate-type reactor as reactor, by use in the presence of a catalyst molecularity oxygen or the gas containing molecularity oxygen recorded in such as Japanese Unexamined Patent Publication 2003-252807 publication, the known method that propane, propylene or isobutene are oxidized can be carried out.In addition, above-mentioned catalyst can utilize known usage to use to record in above-mentioned publication Mo-V-Te Containing Oxide Catalyst, Mo-V-Sb Containing Oxide Catalyst, Mo-Bi Containing Oxide Catalyst and Mo-V Containing Oxide Catalyst etc. are generating the well-known catalysts used in (methyl) acrylic acid gas phase contact oxidation reaction.
In addition, the first manufacture method of reaction product can compatibly use in following gas phase haptoreaction, and this gas phase haptoreaction, as the reaction of the raw material in unstrpped gas in the presence of a catalyst, is attended by exothermic reaction.
In the first manufacture method of reaction product, thermal medium is supplied to heat-transfer pipe by thermal medium feedway, and the temperature of this thermal medium is the temperature of the setting value of the peak temperature of the catalyst layer that to make the peak temperature in the Temperature Distribution of the heat transfer plate axis of reaction time catalizer layer be the first plate-type reactor set when designing.The temperature of such thermal medium controls such as can to utilize the known control method such as FEEDBACK CONTROL based on above-mentioned design load to carry out.The temperature of thermal medium when preferably reacting controls to make the peak temperature of catalyst layer be ± 20 DEG C relative to above-mentioned design load, more preferably carry out above-mentioned control and be ± 10 DEG C to make the peak temperature of catalyst layer relative to above-mentioned design load, preferably carry out above-mentioned control further and be ± 5 DEG C to make the peak temperature of catalyst layer relative to above-mentioned design load.Above-mentioned setting value utilizes experiment when determining the above-mentioned design load of plate-type reactor to try to achieve, or determines in the calculating of simulating based on above computer.In addition, the control of the temperature of thermal medium can utilize above-mentioned thermal medium feedway to carry out.
The preparation method > of < first plate-type reactor
First plate-type reactor is by make the distance between the surface of relative above-mentioned heat transfer plate be that the interval of above-mentioned design load configures above-mentioned heat transfer plate, and utilizes welding etc. to carry out engaging obtaining above-mentioned heat-transfer pipe and above-mentioned thermal medium feedway.Above-mentioned heat transfer plate such as can pass through across the thickness pole member identical with above-mentioned design load heat transfer plate arranged side by side, thus is configured with the interval reaching above-mentioned design load.Above-mentioned pole member is taken out by the gap between heat transfer plate after the joint of heat-transfer pipe and thermal medium feedway.
Or when plate-type reactor has above-mentioned sept, above-mentioned heat transfer plate by the heat transfer plate before joint and sept alternately more thickly being configured, thus can be configured with the interval reaching above-mentioned design load.
Accompanying drawing is used to further illustrate embodiments of the present invention below.
< first embodiment >
Such as shown in Figure 1 to 4, the first plate-type reactor has as lower component: more than 2 heat transfer plates 2, and these more than 2 heat transfer plates 2 are disposed side by side in above-mentioned reaction vessel, and have heat-transfer pipe 1; A pair grip block 3, this pair grip block 3 at least abuts against along the heat transfer plate 2 at the two ends on the axle of heat-transfer pipe 1 and heat transfer plate 2 side by side direction, and on heat transfer plate 2 side by side direction, hold more than 2 heat transfer plates 2; More than 2 retention bar 4, these grip blocks 3 couple together by these more than 2 retention bar 4; Thermal medium feedway 5, this thermal medium feedway 5 abuts against with the two ends of the heat-transfer pipe 1 on heat transfer plate 2, and supplies thermal medium to heat-transfer pipe 1; Gas dispenser 6, this gas dispenser 6 covers the two ends of more than 2 heat transfer plates 2 on the direction of the axle of crosscut heat-transfer pipe 1, and makes the gap circulation of gas between adjacent heat transfer 2; Dividing plate 7, the gap between adjacent heat transfer 2 is divided into 2 of the catalyst that accommodation is filled with upper curtate along the ventilation direction of gas by this dividing plate 7; The breather plug 8 of the lower end of inaccessible each section; Temperature measuring apparatus 9, this temperature measuring apparatus 9 is arranged 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 arranged according to the mode of the top of covering more than 2 heat transfer plates 2.
Heat-transfer pipe 1 is such as be 30 ~ 50mm at the diameter (major diameter, L) axially of heat transfer plate 2, be 10 ~ 20mm at the diameter (minor axis, H) in the direction orthogonal with the axis of heat transfer plate 2; Cross sectional shape is the pipe using circular arc, elliptic arc, rectangle and a polygonal part as the shape of main constitutive requirements.The length of heat-transfer pipe 1 is generally 0.1 ~ 20m, is such as 10m.Fig. 5 show with circular arc be cross sectional shape constitutive requirements, cross sectional shape is leaf heat-transfer pipe.In Fig. 5, the major diameter of heat-transfer pipe represents with L, minor axis represents with H.
Heat transfer plate 2 has the shape that more than 2 heat-transfer pipes 1 link with the ora terminalis of cross sectional shape.Heat transfer plate 2 to be undertaken by the flange of the end to be formed at the arc in two steel plates by two steel plates (mode that this steel plate is formed continuously according to elliptic arc forms) that welding is bonded with each other is formed.Above-mentioned steel plate uses thickness to be below 2mm, to be desirably the steel plate of below 1mm.Precision inspection Check is carried out to the shape of the above-mentioned steel plate after shaping, such as, be that shaping steel plate within ± 1% can directly use relative to the error of form finding design value, relative to the error of form finding design value exceed ± the shaping steel plate of 5% can carry out revising the error that makes relative to form finding design value within ± 2%, and then use.
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, the mode relative with the recessed edge on the surface of the heat transfer plate 2 of the opposing party according to the flange on the surface of the heat transfer plate 2 of a side is come side by side.
Heat transfer plate 2 can be all made up of same heat-transfer pipe 1, also can be made up of the heat-transfer pipe 1 that sectional dimension is different.Such as heat transfer plate 2 can form the top of heat transfer plate 2, middle part and bottom by three kinds of heat-transfer pipes that sectional dimension is different respectively.More particularly, as shown in Figure 7, heat transfer plate 2 can be formed according to three kinds of heat-transfer pipes major axis separately configuration mode in a straight line, such as, for the top of heat transfer plate 2, the part accounting for 20% of height of heat transfer plate 2 is made up of the heat-transfer pipe a that sectional dimension is maximum; For the middle part of heat transfer plate 2, the part accounting for 30% of height of heat transfer plate 2 is made up of the heat-transfer pipe b that sectional dimension is second largest; For the bottom of heat transfer plate 2, the part accounting for 40% of height of heat transfer plate 2 is made up of the heat-transfer pipe c that sectional dimension is minimum; The part accounting for 10% of height of heat transfer plate 2 can be formed by the engaging plate portions of the upper end of heat transfer plate 2 and bottom.It is leaf that the cross sectional shape of heat-transfer pipe a is such as that major diameter (L) is 50mm, minor axis (H) is 20mm, it is leaf that the cross sectional shape of heat-transfer pipe b is such as that major diameter (L) is 40mm, minor axis (H) is 16mm, and it is leaf that the cross sectional shape of heat-transfer pipe c is such as that major diameter (L) is 30mm, minor axis (H) is 10mm.
For heat transfer plate 2, be generally 0.5 ~ 10m in the length of the axis of heat transfer plate 2, be preferably below 2m.When the length of the axis of heat transfer plate 2 is more than 2m, 2 heat transfer plates 2 can be engaged or combinationally use.
As shown in Figures 2 and 3, grip block 3 is a pair plate, such as, be a pair plate of stainless steel manufacture.Grip block 3 is formed larger than heat transfer plate 2, can be combined by retention bar 4 in edge.
As shown in Figure 3, the rod of more than 2 that retention bar 4 connects for through a pair grip block 3, such as, for both ends have the stainless steel rod of screw.As shown in Figure 2 to 4, utilized by grip block 3 nut to be fixed on the heat-transfer pipe 1 (position that above-mentioned heat-transfer pipe periphery a) connects with heat transfer plate 2 top at the both ends of retention bar 4.For grip block 3, retention bar 4 screw arrange in the scope of length, can position be changed be fixed on the direction of clamping heat transfer plate 2.In addition, for retention bar 4, be configured in the vertical direction and position that dividing plate 7 that gap between heat transfer plate 2 configures coincides.A pair grip block 3 and retention bar 4 form above-mentioned plate clamping part.
As depicted in figs. 1 and 2, thermal medium feedway 5 is a pair container connected with the two ends of the heat-transfer pipe 1 of heat transfer plate 2, and it such as has as lower component: a pair stainless steel jacket 11,12 with the opening portion corresponding with the heat-transfer pipe 1 connected; Be located at the mouth of pipe 13 of the supply for thermal medium on chuck and discharge; For adjusting the heat exchanger 14 of the temperature of the thermal medium of being discharged by chuck 11; And for making thermal medium carry out the pump 15 circulated between chuck 11 and heat exchanger 14.Thermal medium feedway 5 uses the seals such as common fixed part and packing ring such as screw and nut, at side edge part and grip block 3 airtight joint mutually of grip block 3.
The inside of chuck 11,12 suitably can be split along the direction of the axle of crosscut heat transfer plate 2 in the mode be communicated with or shield, thus in the heat-transfer pipe 1 of every specific radical, thermal medium is to a direction or rightabout flowing, and thermal medium is reciprocal between chuck 11,12.
In addition, thermal medium feedway 5 such as can as shown in the arrow Y in Fig. 2 be thermal medium in whole heat-transfer pipes 1 by the device of side's chuck 11 to the opposing party's chuck 12 one way flow.
Further, for thermal medium feedway 5, such as, can have thermal medium mixing arrangement in the arbitrary room in the room of more than 2 of the axial shield relative to heat transfer plate 2 in chuck 11,12 or in chuck 11,12.As shown in Figure 6, thermal medium mixing arrangement has and is communicated with the mouth of pipe 16 inside and outside chuck and distributing pipe 17, and this distributing pipe 17 is connected with the mouth of pipe 16 in chuck inside, and extends on the direction orthogonal relative to the flow direction of the thermal medium in chuck.Distributing pipe 17 is such as front end is blocked and be provided with the pipe in the hole of more than 2 on the whole length direction throughout distributing pipe.
Gas dispenser 6 such as can be made up of following reaction vessel cover and following gas vent (mouth of pipe 18), the covering that the end portion of the hood-shaped one-tenth of this reaction vessel and above-mentioned more than 2 heat transfer plates is left, and the two ends of the sidewall of reaction vessel that airtight above-mentioned thermal medium feedway and plate clamping part are formed; 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 the various shapes such as semi-spherical shape, cone shape, rectangular pyramid shape, triangular prism shape, housing.In addition, above-mentioned blow vent can use such as have the upper shed of reaction vessel cover the mouth of pipe and be formed at the common blow vent of flange of its end.Above-mentioned reaction vessel cover arranges a pair relative to the sidewall of above-mentioned reaction vessel usually, and they can be the same or different.In addition, above-mentioned blow vent arranges one usually on reaction vessel cover, but also can arrange more than 2.Further, above-mentioned blow vent arranges a pair 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 parts, these a pair parts the upper edge of grip block 3 and the upper edge of chuck 11,12 and the lower ora terminalis of grip block 3 and chuck 11,12 lower end edge respectively example such as above-mentioned fixed part and seal engage the two ends covering more than 2 heat transfer plates 2 airtightly.Gas dispenser 6 is such as the stainless steel lid of semicylinder (か ま Pot こ) type.Gas dispenser 6 has the mouth of pipe 18 and gateway 19 respectively.By the mouth of pipe 18 of the gas dispenser 6 of a side, gas supplies towards the gap between heat transfer plate 2, and by the mouth of pipe 18 of the lid of the opposing party from above-mentioned gap Exhaust Gas.In above-mentioned plate-type reactor, grip block 3, thermal medium feedway 5 and gas dispenser 6 is by engaging forming reactions container airtightly.
Gateway 19 is that operator to come in and go out switch gate used relative to gas dispenser 6 under the state being provided with gas dispenser 6.The configuration of the mouth of pipe 18 and gateway 19 is not particularly limited, and when gas dispenser 6 is the lid of the semicolumn bodily form, such as shown in Figure 1, the mouth of pipe 18 is located at an end of lid, and the other end of lid is located in gateway 19.Further, for gas dispenser 6, when sharply rising as pressure anomaly or abnormal response time Security Countermeasures, in the main body of the gas dispenser 6 of inlet portion and/or export department or the mouth of pipe 18, the not shown safety device such as safety valve or fracture plate is set.In addition, about gas dispenser 6 and the gateway 19 of reactor outlet side, when the gas generation delay containing reaction product can make generated object decompose or accumulation occurs accessory substance, structure or the additives for reducing delay portion is preferably set.
Dividing plate 7 is arranged between adjacent heat transfer 2 along the ventilation direction of gas in the direction of the axle of crosscut heat-transfer pipe 1, i.e. plate-type reactor.As shown in Figure 7, dividing plate 7 is such as plate-shaped member that abut with the surface of heat-transfer pipe 1, that have sufficient rigidity, and it has the window 20 as rectangle through hole in bottom.Dividing plate 7 is by the sept of the distance maintaining of heat transfer plate 2 at appointed interval.Dividing plate 7 can be arranged with same intervals in plate-type reactor entirety, also can arrange with different interval.Dividing plate 7 is such as set up in parallel with the same intervals of 400mm, and the gap between heat transfer plate 2 forms 2 of 12L volume with upper curtate.
As shown in Figure 8, breather plug 8 has the vent board 21 of the rectangle identical with the cross sectional shape of each section, first skirt section 22 of establishing and being hung down second skirt section 23 of establishing by the long limit of vent board 21 of being hung down by the minor face of vent board 21 downwards downwards.Form the locking window 24 of rectangle in the first skirt section 22 and and be located at the engagement pawl 25 on its side.
Vent board 21 is such as forming the plate of the circular port of 2mm with aperture opening ratio 30%.Locking window 24 is formed with the size with width and the height holding engagement pawl 25.In addition, engagement pawl 25 by two parallel groovings of the lower ora terminalis from the first skirt section 22 laterally bent tabs formed.In a pair relative first skirt sections 22, the locking window 24 of a side is relative with the engagement pawl 25 of the opposing party, and the engagement pawl 25 of a side is relative with the locking window 24 of the opposing party.The window 20 of dividing plate 7 is formed according to the size with width and the height simultaneously comprising locking window 24 and engagement pawl 25.
Breather plug 8 makes vent board 21 upwards insert each section from the lower end of each section.Now engagement pawl 25 is resisted reinforcing laterally and is pressed to dividing plate 7, when arriving window 20, as shown in Figure 9, discharges and enters window 20, be locked to window 20 from the extruding of dividing plate 7.
Such as, for temperature measuring apparatus 9, as shown in Figure 2, in the gap of more than 2 that heat transfer plate 2 is formed, be located at outermost gap and by comparison for inner side any gap in.In addition, for temperature measuring apparatus 9, in a gap between heat transfer plate 2, along the flow direction that is axial, i.e. thermal medium of heat-transfer pipe 1, be arranged on comprise thermal medium entrance near and export near multiple positions.The setting position of temperature measuring apparatus 9 can be determined according to the temperature difference between the thermal medium of of heat transfer plate 2 heat-transfer pipe 1 middle and upper reaches side and the thermal medium in downstream.Such as, when the temperature of thermal medium controls with the unit of 0.5 DEG C, temperature measuring apparatus 9 temperature difference be arranged between the thermal medium of the upstream side of a heat-transfer pipe 1 of heat transfer plate 2 and the thermal medium in downstream is the position of more than 2 DEG C.
As shown in Figure 10, temperature measuring apparatus 9 has: have flexual support 26; The temperature measuring portion 27 of more than 2 that supports by support 26; Extended and the spacer rod 28 of more than 2 connected 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 be connected with flange 29; The cable 31 be connected with connector 30; And be located at the fixing flange 32 of front end of support 26.
The stainless steel tubulation of support 26 to be average thickness of tube wall be 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.Such as, near entrance temperature measuring portion 27 being arranged on reacting gas in catalyst layer, near outlet and be predicted as three positions, place of maximum temperature respective in each conversion zone of each catalyst layer.More particularly, as shown in Figure 10, on the ventilation direction in each gap, temperature measuring portion 27 arranges one respectively, arranges three at the central portion of the first conversion zone formed by heat-transfer pipe a group, arrange three at the central portion of the second reaction zone formed by heat-transfer pipe b group, arrange three on the top of the 3rd conversion zone formed by heat-transfer pipe c, arrange one in the bottom in each gap in the upper end in each gap.
In addition, in each heat-transfer pipe 1 temperature difference of thermal medium be more than 2 DEG C position and be predicted as each catalyst layer each conversion zone in reach the position of maximum temperature can based on using the experimental result of the testing machine of this reactor or determining based on the result of the computer simulation using the softwares such as the gPROMS of STAR-CD, PSE society of CFX, CD adapco society of ANSYS Co., Ltd..
Spacer rod 28 is fixed on the stainless steel bar extended on support 26 and to horizontal direction for cardinal extremity.Spacer rod 28 has the length corresponding to the position in support 26, the length that front end when support 26 is supported in the median plane in each gap with spacer rod 28 contacts with the surface of heat transfer plate 2.Spacer rod 28 arranges three from the central portion of support 26 to base end part, arranges according to the mode alternately contacted with relative each heat transfer plate 2.
For flange 29, in order to support 26 being fixed on the top of reaction vessel, be such as positioned in flange 29 is supported in the predetermined height in reaction vessel flange holding components on.Flange holding components such as to be hung down the bolt established remained on the parts of predetermined altitude by nut by the gas dispenser 6 of upside for inserting, such as by clamping support 26 two steel wires, have bolt hole and support the steel wire holding components of two steel wires and the nut that the steel wire holding components inserting above-mentioned bolt in the hole of bolt is screwed on from bottom formed.Fixing be greater than plectane or the wheel of the diameter in the hole in the vent board 21 of breather plug 8 with flange 32 for had diameter, such as make the front end of support 26 lead to the above described holes of vent board 21 after be fixed on the front end of support.
In the temperature measuring apparatus 9 of Figure 10, in vertical direction, in the bottom in above-mentioned gap, apart from each equidistant position of heat transfer plate 2, the front end of support 26 is fixed on breather plug 8 by fixing with flange 32; And in the upper end in above-mentioned gap, apart from each equidistant position of heat transfer plate 2, utilize above-mentioned flange holding components to fix the cardinal extremity of support 26.By tightening the nut of flange holding components, nut is moved upward, and support 26 is stretched upward by flange holding components, and each spacer rod 28 is linearly under the state of the surface contact with heat transfer plate 2.
In above-mentioned plate-type reactor, by above-mentioned formation, it is arranged side by side at equal intervals that heat transfer plate 2 is such as 14mm (axle base of each heat transfer plate 2 is for 30mm) with the beeline between the outer wall of heat-transfer pipe a.
For heat transfer plate 2, be configured in desired position, in the two ends of this position heat-transfer pipe 1 and chuck 10,11 solder joints by heat transfer plate 2 and sept 7 alternately being configured.Herein, distance between the surface of heat transfer plate 2 is: when being observed heat transfer plate 2 by the gap between heat transfer plate 2 (Fig. 1), on the cross section (Fig. 3 and Fig. 5) of the heat transfer plate 2 when cutting off heat transfer plate 2 along the ventilation direction (B-B ' line in Fig. 1) of gas in above-mentioned gap, the distance between the surface of the heat transfer plate 2 on the direction orthogonal with the equidistant line of axle be positioned at apart from heat transfer plate 2.Heat transfer plate 2 according to heat transfer plate 2 axle vertically, the axle mode in the horizontal direction of heat-transfer pipe 1 is configured, thus such as heat transfer plate 2 surface between the design load of distance, be in the heat transfer plate 2 that is configured of vertical direction according to axle, among distance between the surface of heat transfer plate 2 in the horizontal direction, 20mm is counted with the recessed intermarginal distance of the flange of side's heat transfer plate and the opposing party's heat transfer plate, when the measured value of above-mentioned distance is 19.5 ~ 21mm, now relative to heat transfer plate 2 surface between the difference of design load of distance be-0.5 ~ 1.0mm.
Catalyst filling in each section in the gap between adjacent heat transfer 2.Catalyst such as uses molybdenum (Mo)-bismuth (Bi) series catalysts that maximum average grain diameter is 5mm, shape is annular.In the section formed by heat transfer plate 2 and dividing plate 7, fill the catalyst of the predetermined volume corresponding to the volume of this section.
Gap-fill between heat transfer plate 2 has the state of catalyst 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 by 2 sheet formings, toward each other to joint, Formation cross-section amasss the stream 33,34,35 of three kinds of different thermal mediums.The width of stream 33 is maximum, and therefore the width of catalyst layer 36 is the narrowest between stream 33.The flow path width of stream 34,35 reduces successively compared to stream 33, and therefore the width of catalyst layer 36 broadens successively.
Catalyst layer 36 forms three conversion zones 37,38,39 corresponding to stream 33,34,35.If the mean value of the distance between the heat transfer plate 2 making the direction that the thickness of catalyst layer 36 is and the axle of heat transfer plate 2 is at a right angle, the thickness of the catalyst layer 36 then in conversion zone 37 is such as 8 ~ 15mm, the thickness of the catalyst layer 36 in the conversion zone 38 after conversion zone 37 is such as 10 ~ 20mm, and in the conversion zone 39 after conversion zone 38, the thickness of catalyst layer 36 is such as 15 ~ 30mm.
Under the above-mentioned plate-type reactor of use carries out the catalytic situation of gas phase, reaction temperature is controlled by the temperature of the thermal medium flowing through heat-transfer pipe 1.The temperature of thermal medium is different according to the difference of raw material, product, catalyst type, is usually preferably 200 ~ 600 DEG C.As an example of heat medium temperature, when reaction raw materials gas is C3 ~ C4 unsaturated hydrocarbons, heat medium temperature is 300 ~ 400 DEG C.The temperature being supplied to the thermal medium of each conversion zone carries out determining, controlling independently of one another.When reaction raw materials gas is (methyl) methacrylaldehyde, select the temperature of thermal medium the scopes of 250 ~ 320 DEG C.
The reaction conversion ratio of reaction raw materials gas is particular importance, controls the temperature of thermal medium to obtain desired conversion ratio.If the temperature of catalyst layer is more than allowable temperature when plate-type reactor operates, then can produce that catalyst activity reduces, selection rate reduces, the problems such as increase that underspeed of active or selection rate.So-called " conversion ratio " refers to herein, relative to the quantity delivered of unstrpped gas (such as propylene) being supplied to catalyst layer, is converted into the ratio of the amount of the unstrpped gas of product by reaction; So-called " selection rate " refers to, the ratio of the amount of the unstrpped gas that the amount being converted to the unstrpped gas of target product transforms with respect to reaction.
In order to obtain predetermined conversion ratio, the temperature of thermal medium is controlled, but in order to keep the high-performance of catalyst for a long time, be very important below the maximum temperature of the catalyst layer maximum permissible temperature for used catalyst, it is very important for more preferably in the scope obtaining desired reaction achievement, the maximum temperature of catalyst layer being remained on as far as possible low temperature.
At the conversion zone of 2 ~ 5, respectively to make the peak temperature of catalyst layer be temperature supply thermal medium within above-mentioned setting value ± 10 DEG C, and thermal medium flows in the direction (cross flow direction) rectangular with the flow direction of reacting gas.In a heat-transfer pipe 1, the temperature difference of entrance and exit thermal medium is preferably 0.5 ~ 10 DEG C, is more preferably 2 ~ 5 DEG C.In the form shown in Figure 11, there is the situation of the thermal medium individual flow in each respective root of the heat-transfer pipe 1 in such as stream 33 ~ 35 controlled at predetermined temperature, and also have situation about simultaneously flowing in whole heat-transfer pipes 1 of same conversion zone.In addition, the heat-transfer pipe 1 of certain conversion zone can be also supplied to and the thermal medium of discharging is supplied to the heat-transfer pipe 1 of same or other conversion zone.
As the making precision that it should be noted that is high with the possibility that is associated of reaction achievement, plate-type reactor, the thickness of heat-transfer pipe a ~ c determined for the thickness (distance between the surface of heat transfer plate 2) to catalyst layer 36 and the axle base of 1 pair of heat transfer plate 2.When the axle base of heat transfer plate 2 is constant, the thickness of heat-transfer pipe 1 is excessively thin relative to setting value, if or the axle base of heat transfer plate 2 is excessive relative to setting value, then the thickness (distance between the surface of heat transfer plate 2) of catalyst layer 36 becomes large, effectively can not carry out giving and accepting of heat, correctly can not maintain the temperature of catalyst layer 36 or reaction raw materials.
When the axle base of heat transfer plate 2 is constant, the thickness of thermal medium stream is excessive relative to setting value, if or the axle base of heat transfer plate 2 is too small relative to setting value, then the thickness (distance between the surface of heat transfer plate) of catalyst layer 36 diminishes, giving and accepting of heat becomes efficient, but correctly can not fill the catalyst of setting, can not correctly maintain gas phase haptoreaction.
In above-mentioned plate-type reactor, for thermal medium, the such as thermal medium of flowing 345 DEG C in heat-transfer pipe 1, and flow containing the gas as the propylene of unstrpped gas, molecularity oxygen, steam and inert gas from the gas dispenser 6 of upside, obtain thus containing methacrylaldehyde and acrylic acid reacting gas.For the quantity delivered base feed gas of the unstrpped gas of the reaction product of the yield obtained desired by above-mentioned design load is determined, with the temperature of the thermal medium determined by above-mentioned design load 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 layer 36.
When peak temperature A is within above-mentioned setting value ± 10 DEG C, thermal medium is supplied to heat-transfer pipe 1 with the design temperature of thermal medium and quantity delivered.When peak temperature A is higher than above-mentioned setting value+10 DEG C, thermal medium is supplied to heat-transfer pipe 1 with the setting quantity delivered of the temperature of the design temperature lower than thermal medium and thermal medium.When peak temperature A is lower than above-mentioned setting value-10 DEG C, thermal medium is supplied to heat-transfer pipe 1 with the setting quantity delivered of the temperature of the design temperature higher than thermal medium and thermal medium.Thus by controlling the temperature of thermal medium according to the peak temperature of catalyst layer 36, when not reducing reaction yield, reaction product can be manufactured continuously in the quantity delivered of not feed change gas.
In above-mentioned plate-type reactor, be the heat transfer plate 2 of the steel plate joint within ± 1% owing to using being configured as relative to the error of design load, thus the temperature by controlling thermal medium makes the measured value of the peak temperature of catalyst layer be the setting value of this peak temperature, can maintain the manufacture of reaction product thus under large-duty condition.
In addition, in above-mentioned plate-type reactor, owing to having dividing plate 7, thus from the viewpoint of by heat transfer plate 2 according to heat transfer plate 2 surface between the design load of distance is configured is effective.Further, in above-mentioned plate-type reactor, owing to having dividing plate 7, form 2 in the gap thus between heat transfer plate 2 with upper curtate, can in units of section catalyst filling, thus from the viewpoint of being effective by catalyst uniform filling to above-mentioned gap.
In addition, in above-mentioned plate-type reactor, owing to having temperature measuring apparatus 9, thus can measure the temperature of catalyst layer 36, be effective from the viewpoint of what control to carry out the manufacture of product expeditiously based on the temperature of carrying out thermal medium according to the peak temperature of catalyst layer 36.
In addition, in above-mentioned plate-type reactor, owing to having thermal medium mixing arrangement, thus consider it is effective from the temperature aspect rapidly and critically controlling the thermal medium thermal medium feedway 5.
In addition, in above-mentioned plate-type reactor, owing to having breather plug 8, thus only can extract the catalyst of any section out, be effective 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 having gas dispenser 6 and gateway 19, further because retention bar 4 is configured in the position overlapping with dividing plate 7, thus can utilize the scaffold in packed catalyst operation or maintenance inspection operation or the retention bar 4 as its holding components, be effective from the viewpoint of what carry out operation in plate-type reactor inside expeditiously.
It should be noted that, in the first plate-type reactor, also comprise such, form shown in Figure 12 as disclosed in patent document 2, for example, in this form, in three conversion zones 40,41,42 formed along the flow direction of unstrpped gas, the width of catalyst layer 43 successively expands.
Plate-type reactor is usually difficult to precision and makes well, and such as, for having the same heat-exchangers of the plate type formed, the distance between the surface of usual heat transfer plate has the error of 3 ~ more than 5mm relative to design load.In the first plate-type reactor, can be provided in the plate-type reactor that can control to configure in the error range that controls to react by the temperature of thermal medium heat transfer plate, significantly can expand the possibility that plate-type reactor industrially utilizes.
First plate-type reactor may be used in the reaction under the existence of solid-phase catalyst, phase feed being reacted, carry out when using, having given play to more significant effect under temperature particularly in reactor in use and the very large condition of the difference between the normal temperature carrying out the operation for preparing or check, and more significant effect can have been given play in the following cases: under the condition when unstrpped gas and generation gas are exposed to use for a long time, these gas properties are caused to change, thus the damage of reactor can be produced, when using in such a situa-tion, along with the reaction of unstrpped gas composition, reaction heat enlarges markedly, because heat makes catalyst be easy to deterioration occur, when the temperature treatment of catalyst layer is very important.
< second plate-type reactor >
Second plate-type reactor has: the reaction vessel reacted for making reaction raw materials; There is heat-transfer pipe, more than 2 heat transfer plates be disposed side by side in above-mentioned reaction vessel; To the thermal medium body feeding of above-mentioned heat-transfer pipe supply thermal medium body; And the gap between adjacent heat transfer plate is divided into 2 of the catalyst that accommodation is filled with the dividing plate of upper curtate along the ventilation direction in reaction vessel.
The catalyst layer of more than 2 heat transfer plates and more than 2 is formed in above-mentioned reaction vessel, these more than 2 heat transfer plates are arranged side by side in ventilation direction in reaction vessel, this catalyst layer of more than 2 be the gap of packed catalyst between adjacent heat transfer is formed and arranged side by side in direction of ventilating in reaction vessel.The shell that such as to use relative to the shape of cross section in ventilation direction in reaction vessel be rectangle or the housing that the shape of above-mentioned cross section is circle.
The container that above-mentioned reaction vessel is discharged by the gap between adjacent heat transfer for supplied reaction raw materials, has a pair blow vent usually.Above-mentioned a pair blow vent, on the one hand for being supplied to the supply port of the reaction raw materials of reaction vessel, is the outlet of the reaction product generated in reaction vessel on the other hand.For the form of blow vent, as long as be just not particularly limited by the shape of the discharge of reaction vessel to the supply of reaction vessel and reaction product for reaction raw materials can be carried out.A pair preferred relative setting of blow vent.As such blow vent, can enumerate such as, be located at a pair blow vent at the two ends of shell or housing and a pair following blow vent, this a pair blow vent is formed as cylindric in the inner peripheral portion of the central part and housing that comprise central shaft of housing respectively, and ventilates with the radial reacting fluid that makes at the cross section of housing.
Above-mentioned heat transfer plate comprises more than 2 heat-transfer pipes linking in a direction with the periphery of cross sectional shape or ora terminalis and is formed as tabular.
Disclosed in patent document 1, such heat transfer plate can by utilizing the flange being formed at two ripple plate patterned sides ends to carry out being bonded with each other being formed two the ripple plates forming the patterns such as circular arc, elliptic arc, rectangle continuously.Or the above-mentioned heat-transfer pipe of more than 2 can link in periphery or ora terminalis and be formed by heat transfer plate.Or the above-mentioned heat-transfer pipe of more than 2 can be piled up formation according to the mode connected in periphery or ora terminalis in reaction vessel by heat transfer plate.
The shape of heat transfer plate is determined according to the shape of reaction vessel and size, is generally rectangle.In addition, the size of heat transfer plate is determined according to the shape of reaction vessel and size, such as when for rectangular heat conduction plate, its longitudinal (i.e. connection height of heat-transfer pipe) is 0.5 ~ 5m, is more preferably 1 ~ 3m, its horizontal (i.e. length of heat-transfer pipe) is 0.05 ~ 10m, is more preferably 1 ~ 10m, but in normal circumstances, lateral dimension does not limit.
In reaction vessel adjacent heat transfer can according to the surfaces lips of heat transfer plate toward each other to mode arrange, also can arrange according to the mode that the flange on side's heat transfer plate surface is relative with the recessed edge on the opposing party's heat transfer plate surface.The scope that distance between adjacent heat transfer can be set in 15 ~ 50mm in the mean value of the major axis spacing of the heat-transfer pipe in each heat transfer plate, is more preferably 23 ~ 50mm (in adjacent heat transfer 1.1 ~ 5 times of half value sum of heat-transfer pipe width, be more preferably 1.1 ~ 2 times), to make to form 3 ~ 40mm in the transverse direction of heat-transfer pipe, be more preferably the gap of the width of 3 ~ 15mm between heat transfer plate.From the viewpoint of obtaining high reactivity and high reaction achievement, the distance between heat transfer plate in the mean value of the distance between the major axis of heat-transfer pipe preferably 10 ~ 50mm, be more preferably 10 ~ 40mm, more preferably 20 ~ 35mm.
Consider from the aspect of being carried out the control of raw material reaction by the temperature of thermal medium body adjustment heat-transfer pipe, the heat-transfer pipe in heat transfer plate is not preferably formed as extending along the direction parallel with the ventilation direction in reaction vessel; The direction of the thermal medium body consider from the aspect of being carried out the control of raw material reaction by the temperature of thermal medium body adjustment heat-transfer pipe, the heat-transfer pipe in heat transfer plate is more preferably formed as extending along the direction orthogonal with the ventilation direction in reaction vessel, also namely flowing in heat-transfer pipe is the direction orthogonal with the ventilation direction in reaction vessel.
Above-mentioned heat-transfer pipe by the thermal medium body had in heat-transfer pipe and and the external catalyst layer of heat-transfer pipe between there is the conductivity of heat of heat exchange material formed.As such material, such as stainless steel and carbon steel can be enumerated.The cross sectional shape of heat-transfer pipe can be circular, and can be oval or elliposoidal etc. is intended circular, also can be rectangle.The periphery of the cross sectional shape of so-called heat-transfer pipe refers to circular periphery, and the ora terminalis of the cross sectional shape of so-called heat-transfer pipe refers to intends the circular ora terminalis of longitudinal end or the edge of rectangle.
The section shape and size separately of more than 2 heat-transfer pipes in a heat transfer plate can be that certain value also can be different.For the size of the cross sectional shape of heat-transfer pipe, the width of such as heat-transfer pipe is 3 ~ 50mm, is more preferably 3 ~ 20mm or 5 ~ 50mm, and the height of heat-transfer pipe is 10 ~ 100mm, is more preferably 10 ~ 50mm or 20 ~ 100mm.
For the width of heat-transfer pipe, when the heat of the time per unit of giving and accepting through heat transfer plate or per unit area is little, from the viewpoint of the thickness thickening catalyst layer, get catalyst layer thickness large value increasing catalyst, improve reaction speed, be more preferably 3 ~ 20mm; When the heat of the time per unit of giving and accepting through heat transfer plate or per unit area is large, from the viewpoint of the thickness reducing catalyst layer make heat transfer good, reduce catalytic amount to reduce reaction speed, be more preferably 5 ~ 50mm.In addition, for the height of heat-transfer pipe, when the heat of the time per unit of giving and accepting through heat transfer plate or per unit area is little, the large value of getting catalyst layer thickness from the viewpoint of the thickness thickening catalyst layer increasing catalyst, improve reaction speed, be more preferably 10 ~ 50mm; When the heat of the time per unit of giving and accepting through heat transfer plate or per unit area is large, from the viewpoint of the thickness reducing catalyst layer make heat transfer good, reduce catalytic amount to reduce reaction speed, be more preferably 20 ~ 100mm.
Above-mentioned thermal medium body feeding can for upwards stating the device of heat-transfer pipe supply thermal medium body.As such thermal medium body feeding, such as, can enumerate, thermal medium body is supplied to whole device of more than 2 heat-transfer pipes with a direction; And thermal medium body is supplied to a part for more than 2 heat-transfer pipes with a direction and thermal medium body is supplied in the opposite direction the device of the other parts of more than 2 heat-transfer pipes.Thermal medium body feeding makes thermal medium body inside and outside reaction tube, carry out the device circulated preferably by above-mentioned heat-transfer pipe.Consider from the aspect controlled the reaction reaction vessel, preferred above-mentioned thermal medium body feeding has the device of the temperature for adjusting thermal medium body.
The gap of aforementioned barriers between adjacent heat transfer is arranged along the ventilation direction in reaction vessel, forms 2 with upper curtate in above-mentioned gap.For aforementioned barriers, when being filled with catalyst at each section, as long as the parts of catalyst can be kept at each section.Aforementioned barriers preferably adopts the material same with heat transfer plate to be formed, and preferably has conductivity of heat, and preferably reactivity be there is no for the reaction in reaction vessel, reaction in reaction vessel preferably has heat resistance when being exothermic reaction.In addition, from the viewpoint of what keep the catalyst be filled in each section, aforementioned barriers preferably has rigidity.As such dividing plate, plate, square rod, pole, net, mineral wool and ceramic wafer that such as stainless steel manufactures can be enumerated.
The shape of aforementioned barriers can for catalyst is remained on the section formed by each dividing plate shape, can for connect with heat-transfer pipe shape, also can for closely sealed shape.Further, for aforementioned barriers, from the viewpoint of what keep the catalyst be filled in each section, the shape preferably connected with the surface of the outer wall of respective heat-transfer pipe, is more preferably the shape closely sealed with the surface of the outer wall of heat-transfer pipe.In addition, from the viewpoint of easily arranging dividing plate, aforementioned barriers preferred front view is the shape of the quadrangle of width in the beeline had between adjacent heat transfer.
For aforementioned barriers, from the viewpoint of accurately and easily carrying out the filling of catalyst to a section, the interval being preferably 1 ~ 100L according to the volume of the section formed by dividing plate is arranged.The section formed by dividing plate volume separately can be the same or different, preferably identical from the aspect accurately and easily to whole section catalyst filling.The volume of an above-mentioned section is more preferably 1.5 ~ 30L, more preferably 2 ~ 15L, is further preferably 3 ~ 15L, more more preferably 5 ~ 10L.In addition, from same aspect, the distance (interval of dividing plate) between preferred separator is 0.1 ~ 1m.In addition, the length being spaced apart the above-mentioned section axially of above-mentioned heat-transfer pipe of dividing plate, and be form above-mentioned section adjacent dividing plate between distance, or form above-mentioned section, distance between the internal face of reaction vessel that heat-transfer pipe is connected to and dividing plate.
Aforementioned barriers can suitably be arranged on gap between heat transfer plate according to the proterties of dividing plate.The dividing plate of shape of the width such as having flexual dividing plate or have the beeline between heat transfer plate can by being inserted into gap between the adjacent heat transfer in more than 2 heat transfer plates being set in advance in reaction vessel and the gap be located between heat transfer plate.In addition, for the dividing plate of the closely sealed shape on heat transfer plate surface, when heat transfer plate is arranged in reaction vessel, can by being arranged alternately heat transfer plate and dividing plate and the gap be located between heat transfer plate.
The catalyst being filled into above-mentioned section can be used in gas-phase reaction the common granular catalyst in the gap be filled between pipe or heat transfer plate.Catalyst can be that one also can for two or more.As such catalyst, catalyst that such as particle diameter (most major diameter) is 1 ~ 20mm can be enumerated and particle diameter (most major diameter) be 3 ~ 20mm, proportion is the catalyst of 0.7 ~ 1.5.In addition, as the shape of catalyst, known shape can be used, such as, can enumerate spherical, cylindric, Raschig ring shape, saddle.For the shape of catalyst, when aforementioned barriers is formed as the shape on the not closely sealed surface at heat transfer plate, from the viewpoint of preventing catalyst from being leaked by above-mentioned section, the most minor axis being preferably catalyst is greater than the shape between heat transfer plate and the gap of dividing plate; When aforementioned barriers is formed as the shape on the not closely sealed surface at heat transfer plate, be more preferably the shape of the most path of 1.2 ~ 2 times of the maximum in the gap had between dividing plate and heat transfer plate.
Catalyst to the filling in the gap between adjacent heat transfer by carrying out to each section catalyst filling.In each section, can by the catalyst of the capacity equal quantities with a section being filled into continuously or discontinuously the filling carrying out catalyst in a section.The suitable occupied state of catalyst such as can be judged with the comparing of calculated value of the above-mentioned upper surface of each section by the measured value of above-mentioned upper surface in the contrast of the position of the upper surface (terrace) of catalyst (catalyst layer) of filling between section or each section.
In the second plate-type reactor, also can have other constitutive requirements except above-mentioned constitutive requirements further.As other such constitutive requirements, can enumerate such as: reveal peventing member (such as breather plug), these parts have aeration, are located at the end of the heat transfer plate in the downstream in the ventilation direction in above-mentioned reaction vessel, and for preventing the leakage of catalyst from reaction vessel of filling; And latch for printed circuit (the dividing plate fastener for fixing aforementioned barriers), these parts are located at an end of aforementioned barriers, and for fastening with above-mentioned leakage peventing member or heat transfer plate.
Above-mentioned breather plug is make the aeration of each section and the retentivity of catalyst and the parts deposited, and it is the parts of the end in the ventilation direction being detachably fixed on each section.As long as breather plug can prevent catalyst from being spilt by each section, the end of the upstream side in the ventilation direction in each section can be located at, also can be located at the end in downstream, can also both ends be located at.In addition, breather plug entirety can have aeration, also only can have aeration to the ventilation direction of each section.It should be noted that, so-called typically refer to passing through of the gas of one of state as reaction raw materials or reaction product, in this manual, when the state of reaction raw materials or reaction product is fluid (such as the liquid) beyond gas, so-called ventilation also refers to passing through of this fluid.
From the viewpoint of the aeration guaranteeing each section, the aperture opening ratio of preferred above-mentioned breather plug to the ventilation direction of each section be more than 10%.From the viewpoint of when preventing from further breather plug being fixed on section end, the pressure loss occurs, above-mentioned aperture opening ratio is more preferably more than 20%, more preferably more than 30%.
In addition, for above-mentioned breather plug, consider from aspect catalyst remained on each section, preferably the aperture in the ventilation direction of each section is below 5mm, is more preferably below 3mm, more preferably below 1mm.
Above-mentioned breather plug can be made up of the more than one parts with aeration.As above-mentioned breather plug, can enumerate such as, the vent boards such as the net of tabular or porous plate; This vent board is configured as the air funnel of the shape of tubular; There are the parts in above-mentioned vent board and part or all skirt section vertically arranged relative to vent board at its periphery; And to have cross sectional shape be circular or the first air funnel of rectangle and be contained in the inner side of the first air funnel and the aeration sleeve pipe of second air funnel that can be free to slide.From the viewpoint of the sufficient intensity that can obtain for keeping catalyst, preferred above-mentioned air funnel, the parts with skirt section and aeration sleeve pipe.From the viewpoint of the handling easily carrying out each section end, preferred above-mentioned parts with skirt section further.
Have in the parts in skirt section above-mentioned, from the viewpoint of preventing catalyst from being spilt by each section, preferred above-mentioned vent board is the shape identical with the cross sectional shape of each section.For above-mentioned skirt section, from the viewpoint of be easy to carry out breather plug can freely load and unload fixing, preferably in a pair skirt section that a part for vent board periphery connects as such as relative with each section dividing plate or heat transfer plate to arrange above-mentioned skirt section; From the viewpoint of the intensity improving breather plug, be preferably located at the whole of the periphery of vent board.In addition, the mode that skirt section can be outstanding according to the side, two sides to vent board is arranged, and also can arrange according to only outstanding to the one side side of vent board mode.
Above-mentioned breather plug is detachably fixed in the end of each section.From being easy to carry out the fixing of breather plug and the aspect dismantled and consider with the aspect enough keeping the intensity of catalyst to fix breather plug, for detachably fixing formation preferably the first fastener and the second fastener, this first fastener is located at section side, i.e. heat transfer plate and/or dividing plate; This second fastener can engage with this first fastener with freely loading and unloading, and is located at breather plug.As the first and second fasteners, can enumerate the pawl of such as this hole approach axis reinforcing of Kong Yuxiang, Yi Jikong, screw bolt and nut, etc.Consider from the aspect of burn-back preventing the temperature of reaction vessel higher, preferably the first and second fasteners are the such simple and easy formation of above-mentioned hole and pawl.
The material that above-mentioned breather plug has abundant rigidity by the maintenance for catalyst is formed.As such material, metal and the potteries such as such as stainless steel can be enumerated.From heat resistance and resistance to reactive aspect, optimizing breathing bolt adopts the material identical with heat transfer plate to be formed.
In addition, the catalyst being filled in each section can be extracted out with section unit by taking out catalyst by the end of section after dismounting breather plug.
Accompanying drawing is used to further illustrate plate-type reactor of the present invention below.
< second embodiment >
As shown in Figure 13 ~ 15, the second plate-type reactor has: the shell 44 of rectangle; There is heat-transfer pipe 1 and in shell 44 relative more than 2 heat transfer plates 2 be arranged side by side; Hold the thermal medium body accommodation section 45 being supplied to the thermal medium body of heat-transfer pipe 1; Gap between adjacent heat transfer 2 is divided into along the ventilation direction in shell 44 and fills and keep 2 of catalyst with 2 of upper curtate 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 circulated is carried out for making the thermal medium body of thermal medium body accommodation section 45; And the temperature adjustment device 47 for adjusting the temperature of the thermal medium body circulated.
For shell 44, its Formation cross-section shape is the vent passage of rectangle, is equivalent to above-mentioned reaction vessel.In shell 44, there is in the top and bottom of shell 44 relative a pair blow vent 48,48 '.Heat-transfer pipe 1 is the cross sectional shape that such as major diameter is 30 ~ 50mm, minor axis is 10 ~ 20mm is oval pipe.
Heat transfer plate 2 has the shape that more than 2 heat-transfer pipes 1 link with the ora terminalis of cross sectional shape.Heat transfer plate 2 is bonded with each other by making two the ripple plates formed continuously by elliptic arc in the flange of the arc end being formed in two ripple plates and is formed.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 is carried out according to the mode that the flange on the surface of the heat transfer plate 2 of a side is relative with the recessed edge on the surface of the heat transfer plate 2 of the opposing party side by side.
As shown in figure 16, heat transfer plate 2 on top, middle part and bottom comprise three kinds of different heat-transfer pipe a ~ c of sectional dimension respectively.Heat transfer plate 2 is according to by the major axis of heat-transfer pipe a ~ c, the mode be placed on a straight line is formed.In addition, such as heat-transfer pipe a forms the heat transfer plate 2 accounting for the part of 20% of height, the heat transfer plate 2 accounting for the part of 30% of height of heat-transfer pipe b formation heat transfer plate 2, the heat transfer plate 2 accounting for the part of 40% of height of heat-transfer pipe c formation heat transfer plate 2 of heat transfer plate 2.The part accounting for 10% of height of heat transfer plate 2 is formed with the engaging plate portions of the upper end of heat transfer plate 2 and bottom.
The cross sectional shape being formed at the heat-transfer pipe a on the top of heat transfer plate 2 is major diameter is 50mm, minor axis is the ellipse of 20mm, the cross sectional shape being formed at the heat-transfer pipe b at the middle part of heat transfer plate 2 is major diameter is 40mm, minor axis is the ellipse of 16mm, and the cross sectional shape being formed at the heat-transfer pipe c of the bottom of heat transfer plate 2 is major diameter is 30mm, minor axis is the ellipse of 10mm.
It should be noted that, heat transfer plate 2 can with different spacing parallel arrangings in reaction vessel entirety, but in the plate-type reactor of Figure 13, heat transfer plate 2 is arranged side by side with same intervals (beeline between the outer wall of such as heat-transfer pipe a is 14mm (the major axis spacing of the heat-transfer pipe of each heat transfer plate 2 is for 30mm)).
Thermal medium body accommodation section 45 is provided at the container of a pair relative wall of shell 44, supply port for supplying from thermal medium body to each heat-transfer pipe 1 is formed at above-mentioned wall, such as in reaction vessel entirety, according to thermal medium body via the mode of heat-transfer pipe 1 at 45 Tortuous flow in thermal medium body accommodation section, in short transverse, thermal medium body accommodation section 45 is divided into multiple.
Dividing plate 7 is arranged along the ventilation direction in shell 44 between adjacent heat transfer 2.Dividing plate 7 can be arranged with different intervals in reaction vessel entirety, but in the plate-type reactor of Figure 13, dividing plate 7 forms the section of 23L volume side by side with same intervals (such as 1,000mm).The interval that arranges of dividing plate 7 is preferably 5cm ~ 2m, is more preferably 10cm ~ 1m.From the viewpoint of carrying out the filling to the filler in gap with section unit and carrying out accurately and to be easy to packed catalyst, the volume of the section between heat transfer plate and dividing plate is preferably 1 ~ 100L, is more preferably 1.5 ~ 30L.
For dividing plate 7, when each section is filled with catalyst, use the parts that the catalyst of filling can be remained on each section.As shown in Figure 17 ~ 19, dividing plate 7 can use to be had and the plate of the shape of the concavo-convex closely sealed lateral margin on the surface of heat transfer plate 2 or net.
In addition, for dividing plate 7, as long as the catalyst being filled into each section can not drain to adjacent section by the gap between dividing plate 7, the parts connecting with the heat-transfer pipe a of adjacent heat transfer 2, do not abut against with flange and the recessed edge of other heat-transfer pipe b and c of heat transfer plate 2 can be used, as shown in figs 20 and 21, the diameter of the beeline had between adjacent heat transfer 2 or the pole of width or square rod can be used.
Further, as shown in figure 18, dividing plate 7 can for having the net of the mesh less than the size of filled catalyst particle, as long as the catalyst being filled into each section can not drain to adjacent section, also can as shown in figure 19 for having the net of the mesh most minor axis of the such as catalyst (less than 0.8 times) being greater than catalyst size.
When two adjacent heat transfer plates 2 carry out arranged side by side according to the mode that the flange of side's heat transfer plate 2 is relative with the recessed edge of the opposing party's heat transfer plate 2, as shown in figure 22, dividing plate 7 can use the lateral margin of dividing plate 7 sawtooth template that is outstanding to the recessed edge of heat transfer plate 2, that separate from the flange of heat transfer plate 2 or net.For such dividing plate 7, during 0.9 ~ 1.5 times of the half value sum that the distance of two heat transfer plates 2 that the mode relative with the recessed edge of the opposing party when the flange according to a side the is arranged side by side mean value of the major axis spacing of heat-transfer pipe 1 (in each heat transfer plate 2) is the maximum minor axis of heat-transfer pipe in each heat transfer plate 2, compatibly can use such dividing plate 7.
As shown in Figure 17 ~ 19 and Figure 22, when heat transfer plate 2 is located at shell 44, by the dividing plate 7 being arranged alternately heat transfer plate 2 and abut against with it, thus the dividing plate 7 had with the shape of the concavo-convex lateral margin connected on the surface of heat transfer plate 2 is located between two heat transfer plates 2.As shown in Figure 20 and Figure 21, have the diameter of the beeline between adjacent heat transfer 2 or width dividing plate 7 can by be arranged alternately heat transfer plate 2 and and its dividing plate 7 abutted against and be located between two heat transfer plates 2, also can by being inserted into and having arranged between the adjacent heat transfer 2 of the heat transfer plate 2 established.Net or the such flexual dividing plate 7 that has of sheet metal also can by being inserted into and having arranged between the adjacent heat transfer 2 of the heat transfer plate 2 established.
Perforated plate 10,46 is the plate in the hole of 0.20 ~ 0.99 times arranging the most major diameter that diameter is filled catalyst with the aperture opening ratio of 20 ~ 99% respectively.In the plate-type reactor of Figure 13, in order to prevent the ventilation to the gap be configured between outermost heat transfer plate 2 and the wall of shell 44, as shown in figure 15, according to obturation by the mode of the ora terminalis to the gap of the wall of shell 44 that are configured at outermost heat transfer plate 2 to form perforated plate 10,46.
Pump 15 uses the device can carrying the thermal medium body of desired temperature.In addition, in temperature adjustment device 47, the device such as heat exchanger that the temperature of thermal medium body can be controlled in desired temperature is used.Thermal medium body accommodation section 45, pump 15 and temperature adjustment device 47 form thermal medium body feeding.
Catalyst to the filling between heat transfer plate 2 by carrying out to each section catalyst filling.Because the section formed by heat transfer plate 2 and dividing plate 7 all has identical volume, thus fill the catalyst with the capacity equivalent capability of a section (be such as the volume of 95 ~ 100% relative to a section capacity) to each section.
The good occupied state of catalyst can be judged by the comparison of the comparing of the theoretical value of the height during catalyst of filling scheduled volume and measured value (such as measured value is within 10% relative to the error of theoretical value) or the packed height by the catalyst between each section (difference of the packed height such as between each section be 2% of packed height within).
In addition, the hole that dividing plate 7 has the hole hanging over perforated plate 46 or the end being located at heat transfer plate 2 or the hook of taking turns on such holding section, carry out tensioning by this hook being locked on holding section (Zhang Let be set) dividing plate 7, also can be located at the gap between adjacent heat transfer 2 thus.If utilize such formation, then material mineral wool etc. without conformality is used for dividing plate 7.
Above-mentioned plate-type reactor owing to having dividing plate 7, thus by with section unit catalyst filling under constant state, can in reactor monolith uniform filling catalyst.Therefore, compared with the filling to the catalyst between the heat transfer plate 2 not forming such section, the occupied state (such as packed density, voidage) can more easily carried out between accurate relative to design load, each section of catalytic amount can be the filling of homogeneous.
In addition, for above-mentioned plate-type reactor, because the whole sections formed by heat transfer plate 2 and dividing plate 7 have identical capacity, catalyst thus used in a packed catalyst operation is certain.Therefore, with compared with the packed catalyst between the heat transfer plate 2 not forming such section, the filling operation of catalyst can more promptly be carried out.
Further, because above-mentioned plate-type reactor has dividing plate 7, thus can judge the occupied state of catalyst with section unit.Therefore, when the occupied state of catalyst is bad, by again only to being judged as bad section catalyst filling, thus the occupied state of catalyst can be revised.Therefore, with compared with the packed catalyst between the heat transfer plate 2 not forming such section, the adjustment of packed catalyst operation can more easily be carried out.
< the 3rd embodiment >
As shown in Figure 23 ~ 25, in the second plate-type reactor, such as, replace perforated plate 46 and have in aeration and more than 2 breather plugs 8 of the bottom of inaccessible each section, in addition, there is the formation same with the plate-type reactor of above-mentioned second form.
In the present embodiment, shell 44 Formation cross-section shape is the vent passage of rectangle, is equivalent to above-mentioned reaction vessel.Shell 44 has relative a pair blow vent 48,48 ' in the top and bottom of shell 44, and is made up of the outer casing end 49 containing blow vent 48, outer casing end 49 ' containing blow vent 48 ' and the housing main body that holds heat transfer plate 2.Outer casing end 49,49 ' detachably connects relative to housing main body separately.Heat-transfer pipe 1 is the cross sectional shape that such as major diameter is 20 ~ 100mm, minor axis is 5 ~ 50mm is oval pipe.
Heat transfer plate 2 has the shape that more than 2 heat-transfer pipes 1 link with the ora terminalis of cross sectional shape.Heat transfer plate 2 is by by elliptic arc continuously and two the ripple plates formed to be bonded with each other in the flange of the arc end being formed in two ripple plates and to be formed.Adjacent heat transfer 2 can according to surfaces lips toward each other to mode arranged side by side, but in the plate-type reactor of Figure 23, the mode relative with the recessed edge on the surface of the opposing party's heat transfer plate 2 according to the flange on the surface of side's heat transfer plate 2 is arranged side by side.
Such as, as shown in figure 16, heat transfer plate 2 on top, middle part and bottom comprise three kinds of different heat-transfer pipe a ~ c of sectional dimension respectively.Heat transfer plate 2 is formed according to the major axis configuration mode in a straight line of heat-transfer pipe a ~ c.In addition, in the present embodiment, such as heat-transfer pipe a forms the heat transfer plate 2 accounting for the part of 30% of height, the heat transfer plate 2 accounting for the part of 25% of height of heat-transfer pipe b formation heat transfer plate 2, the heat transfer plate 2 accounting for the part of 45% of height of heat-transfer pipe c formation heat transfer plate 2 of heat transfer plate 2.
The cross sectional shape being formed at the heat-transfer pipe a on the top of heat transfer plate 2 is major diameter is 50mm, minor axis is the ellipse of 20mm, the cross sectional shape being formed at the heat-transfer pipe b at the middle part of heat transfer plate 2 is major diameter is 40mm, minor axis is the ellipse of 16mm, and the cross sectional shape being formed at the heat-transfer pipe c of the bottom of heat transfer plate 2 is major diameter is 30mm, minor axis is the ellipse of 10mm.
It should be noted that, in the present embodiment, heat transfer plate 2 can with different spacing parallel arrangings in reaction vessel entirety, but in the plate-type reactor of Figure 23, heat transfer plate 2 is arranged side by side with same intervals (beeline between the outer wall of such as heat-transfer pipe a is 5mm (the major axis spacing of the heat-transfer pipe of each heat transfer plate 2 is for 25mm)).
Thermal medium body accommodation section 45 is identical with the thermal medium body accommodation section 45 in above-mentioned second method.
Dividing plate 7 is arranged along the ventilation direction in shell 44 between adjacent heat transfer 2.Dividing plate 7 can be arranged with different intervals in reaction vessel entirety, but in the plate-type reactor of Figure 23, arranged side by side with same intervals (such as 500mm), form the section of 25L volume.In present embodiment, as shown in figure 26, dividing plate 7 such as having the stainless steel making sheet with the shape of the concavo-convex closely sealed lateral margin on the surface of heat transfer plate 2, has window 20 in bottom.
As shown in figure 27, breather plug 8 is located at the bottom of each section.Breather plug 8 such as shown in figure 28, has the vent board 21 of the identical rectangle of the cross sectional shape of each section, first skirt section 22 of establishing and being hung down second skirt section 23 of establishing by the long limit of vent board 21 of being hung down by the minor face of vent board 21 downwards downwards.In the first skirt section 22, as shown in figure 28, form the locking window 24 of rectangle and and be located at the engagement pawl 50 on its side.
As shown in figure 29, breather plug 8 is the shape launched in vent board 21 and each skirt section 22 and 23, using formed in skirt section 22 locking window 24 and as the stainless steel making sheet of the grooving of engagement pawl 50 between vent board 21 and each skirt section 22,23 border bending, and by being welded at the edge in each skirt section, thus form breather plug 8.Vent board 21 is such as forming the plate in the hole of the circle of 2mm with aperture opening ratio 30%.
In the first skirt section 22, two parallel groovings of the lower ora terminalis from the first skirt section 22 are bent projection and are formed by engagement pawl 50 laterally.In each first skirt section 22, locking window 24 is identical setting with engagement pawl 50 relative to the position relationship of vent board 21 separately.Therefore, in a pair relative first skirt sections 22, the locking window 24 of a side is relative with the engagement pawl 50 of the opposing party, and the engagement pawl 50 of a side is relative with the locking window 24 of the opposing party.In addition, locking window 24 is formed according to the size with width and the height holding engagement pawl 50, and the window 20 of dividing plate 7 is formed according to the size with width and the height simultaneously comprising locking window 24 and engagement pawl 50.
Breather plug 8 makes vent board 21 upwards insert in each section from the lower end of each section.Now engagement pawl 50 is resisted reinforcing laterally and is pressed to dividing plate 7, when arriving window 20, as shown in figure 30, discharges and enters window 20, be locked to window 20 from the extruding of dividing plate 7.Window 20 is equivalent to the first fastener, and engagement pawl 50 is equivalent to the second fastener.
In the present embodiment, perforated plate 10 is the plate in the hole of 0.3 ~ 0.8 times of the most major diameter that to arrange diameter be filled catalyst with the aperture opening ratio of 20 ~ 40%.In the plate-type reactor of Figure 23, for perforated plate 10, in order to prevent the ventilation to the gap be configured between outermost heat transfer plate 2 and the wall of shell 44, as shown in figure 25, perforated plate 10 is formed according to obturation from the mode of the ora terminalis to the gap of the wall of shell 44 that are configured at outermost heat transfer plate 2.
Pump 15 is identical with temperature adjustment device 47 with the pump 15 in above-mentioned first method with temperature adjustment device 47.Thermal medium body accommodation section 45, pump 15 and temperature adjustment device 47 form thermal medium body feeding.
Catalyst to the filling between heat transfer plate 2 by carrying out to each section catalyst filling.The section formed due to heat transfer plate 2 and dividing plate 7 all has same volume, thus in the present embodiment, such as, the catalyst of the capacity equal with the capacity of a section (be such as the volume of 97 ~ 103% relative to the capacity of a section) is filled to each section.
In the present embodiment, the good occupied state of catalyst can be judged by the comparison of the packed height of the catalyst between the comparing of the theoretical value of the packed height of catalyst and measured value (such as measured value is within 3% relative to the error of theoretical value) or each section (difference of the packed height such as between each section be 5% of packed height within).
When the occupied state of the catalyst of one section is bad, extract the breather plug 8 of this section, only extract from the lower end of this section the catalyst be filled into this section out.For the window 20 of dividing plate 7, because it is according to comprising locking window 24 and the size of engagement pawl 50 is formed when breather plug 8 is fixed, thus window 20 carries out opening across dividing plate 7 relative to the locking window 24 of adjacent two breather plugs 8 and engagement pawl 50.Further, because locking window 24 is formed with the size comprising engagement pawl 50, the locking window 24 of the side thus in two breather plugs 8 that dividing plate 7 is adjacent is relative to engagement pawl 50 opening of the opposing party, and the locking window 24 of the opposing party is relative to engagement pawl 50 opening of a side.Thus, the engagement pawl 50 engaged is not blocked by adjacent breather plug 8 relative to the space of the downside of vent board 21, thus in the lower side space of vent board 21, can directly press engagement pawl 50.Thus for breather plug 8, such as shown in figure 31, front end is used to have the instrument that can be inserted into the hook engaged in window 24, by across the adjacent locking window 24 of breather plug 8 of dividing plate 7 and the window 20 of dividing plate 7, utilize above-mentioned hook to press engagement pawl 50, can be unloaded by the locking removed between engagement pawl 50 and window 20.
After catalyst is taken out, again breather plug 8 inserted from the lower end of this section and fix, and to this section catalyst filling, the filling of catalyst in each section can be re-started thus.
Above-mentioned plate-type reactor, owing to having dividing plate 7, thus passes through with section unit catalyst filling under constant state, can by catalyst uniform filling in reactor monolith.Therefore, with compared with the packed catalyst between the heat transfer plate 2 not forming such section, the accurate filling of catalyst can more easily be carried out.
In addition, in above-mentioned plate-type reactor, because the whole sections formed by heat transfer plate 2 and dividing plate 7 have identical capacity, catalyst thus used in a packed catalyst operation is certain.Therefore, with compared with the packed catalyst between the heat transfer plate 2 not forming such section, the filling operation of catalyst can more promptly be carried out.
Further, because above-mentioned plate-type reactor has dividing plate 7, thus can judge the occupied state of catalyst with section unit.Therefore, when the occupied state of catalyst is bad, by again only to being judged as bad section catalyst filling, the occupied state of catalyst can be revised.Therefore, with compared with the packed catalyst between the heat transfer plate 2 not forming such section, the adjustment of packed catalyst operation can more easily be carried out.
In addition, in above-mentioned plate-type reactor, owing to having breather plug 8, the extraction of catalyst can therefore easily be carried out with section unit.Therefore, when the occupied state of catalyst is bad, unloads the breather plug being judged as bad section, catalyst is extracted out by section, again to this section catalyst filling, easily can revise the occupied state of the catalyst of particular section thus.Therefore, with compared with the packed catalyst between the heat transfer plate 2 not forming such section, the adjustment of the filling operation of catalyst can further easily be carried out.
In addition, because breather plug 8 has vent board 21 and first and second skirt sections 22,23 of rectangle, thus from the viewpoint of the abundant intensity obtaining supporting the catalyst layer of each section is excellent.In addition, because breather plug 8 is obtained by die-cut, the bending of steel plate and welding, so excellent breather plug 8 can thus easily be obtained.
In addition, for breather plug 8, there is in a pair relative first skirt sections 22 locking window 24 and engagement pawl 50 separately, in a pair relative first skirt sections 22, the locking window 24 of one side is relative with the engagement pawl 50 of the opposing party, the engagement pawl 50 of one side is relative with the locking window 24 of the opposing party, thus in the breather plug 8 that dividing plate 7 is adjacent, not overlapping or when abutting in the engagement pawl 50 outstanding by each breather plug 8, breather plug 8 is fixed with sufficient intensity, and easily carry out the dismounting of breather plug 8, consider it is excellent from above-mentioned viewpoint.
Further, the window 20 due to dividing plate 7 comprises the size engaging window 24 and engagement pawl 50 when breather plug 8 is fixed to be formed, and arbitrary engagement pawl 50 of two breather plugs 8 thus connected with dividing plate 7 is and detachably engages.Like this, owing to arranging the dividing plate 7 with the window 20 of single specification, thus from the viewpoint of the free construct for handling forming breather plug 8 at low cost, above-mentioned plate-type reactor is excellent.
In addition, in above-mentioned plate-type reactor, owing to fixing breather plug 8 in the below of vent board 21 by the contact that the contact area that the locking between engagement pawl 50 and window 20 is such is little, thus consider it is excellent from the aspect prevented for the burn-back between the engagement pawl 50 during reaction the such higher temperatures condition of oxidation reaction and window 20.
It should be noted that, in above-mentioned plate-type reactor, be that the window 20 as the 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 be set in the same manner as the plate-type reactor of Figure 23.So, for breather plug, even without dividing plate, also by utilizing the bottom of heat transfer plate 5 detachably fixedly to engage.Further, the second fastener can be set at this two place, bottom of the bottom of dividing plate 7 and heat transfer plate 5, in this case, from the viewpoint of improve breather plug constant intensity be effective.
In addition, for dividing plate, such as, various dividing plate can be used according to the different of distance between the kind of the second fastener or setting place, the size in gap generated between dividing plate from heat transfer plate, heat transfer plate.As such dividing plate, such as, can enumerate: having with the net of the shape of the concavo-convex mutually closely sealed lateral margin on the surface of heat transfer plate 2, there is the diameter of the beeline between adjacent heat transfer 2 or the plate of width as shown in Figure 18 and Figure 19; Or pole as shown in Figure 20 and Figure 21 or square rod; As shown in figure 22, the lateral margin of dividing plate 7 to the recessed edge of heat transfer plate 2 outstanding and the sawtooth template separated with the flange by heat transfer plate 2 or net; And not there are based on mineral wool etc. the parts of the material of conformality.
In the present embodiment, dividing plate as shown in Figure 18 and Figure 19 compatibly can be used when mesh the most major diameter of the such as catalyst (less than 0.5 times) of the size of the degree that the netting gear that such as this dividing plate is used has catalyst to spill.The mesh of the net that dividing plate is used is preferably dimensioned to be the mesh (order Open I) of less than 0.8 times of the most path of catalyst.
In addition, in the present embodiment, between heat transfer plate and dividing plate, do not form catalyst when spilling the gap of the width of degree, compatibly can use dividing plate as shown in Figure 20 and Figure 21.In addition, in the present embodiment, 0.9 ~ 1.5 times of the half value sum that the distance (mean value of the major axis spacing of the heat-transfer pipe 1 in each heat transfer plate 2) of the flange of a side two heat transfer plates 2 arranged side by side with relative form with the recessed edge of the opposing party is the maximum minor axis of the heat-transfer pipe in each heat transfer plate 2 time, compatibly can use dividing plate as shown in figure 22.
For dividing plate, when not being provided with the second fastener in such as dividing plate, also can use above-mentioned arbitrary dividing plate.In addition, when such as the second fastener is window, the plate-shaped member that the window that can support breather plug can be set can be used.This is external when such as the second fastener is window, and dividing plate can use the mesh members of the mesh with the sufficient size used as above-mentioned window.
For such as Figure 26,18,19 and Figure 22 shown in, there is the dividing plate with the shape of the concavo-convex lateral margin connected 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 abutted against be located between two heat transfer plates.For shown in Figure 20 and Figure 21, there is the diameter of the beeline between adjacent heat transfer or the dividing plate of width, can by be arranged alternately heat transfer plate and and its dividing plate abutted against and be located between two heat transfer plates, also can by being inserted into and having arranged between the adjacent heat transfer of the heat transfer plate established.Net or cloth or the such flexual dividing plate that has of sheet metal also can by being inserted into and having arranged between the adjacent heat transfer of the heat transfer plate established.
In addition, the hole that dividing plate has the hole hanging over breather plug 8 or the end being located at heat transfer plate 2 or the hook of taking turns on so extra fastener, carry out tensioning arrange dividing plate by this hook being locked on fastener, also can be located at the gap between adjacent heat transfer 2 thus.Preferably such formation of dividing plate is used for from the viewpoint of material mineral wool etc. without conformality.
In addition, for the breather plug 8 in above-mentioned plate-type reactor, as shown in figure 32, also can not use engagement pawl 50 and use front end to have the breather plug of the engagement pawl 51 connected with the lower surface of window 20.From aspect breather plug being firmly fixed at each section, further preferably such breather plug.In addition, for the breather plug with engagement pawl 51, from the viewpoint of also preventing during plate-type reactor Long-Time Service that breather plug from falling, catalyst comes off by the gap between heat transfer plate is also effective.
In addition, for breather plug, as long as have the window 20 suitable free construct for handling such with engagement pawl 50, the breather plug of various form can just be used.As such breather plug, such as can enumerate the cylinder formed with net or vent board as shown in figure 33, the plate with passage as shown in figure 34, as shown in Figure 35 and Figure 36 support the parts of shape of vent board or net with a pair skirt section, the parts of box like that the surface as shown in Figure 37 and Figure 38 is made up of net.
Further, for the breather plug of other form based on such form, the breather plug with the sleeve structure of the first breather pipe 52 and the second breather pipe 53 as shown in figure 39 can be enumerated, described first breather pipe 52 has aeration relative to the ventilation direction of each section, described second breather pipe 53 has aeration relative to the ventilation direction of each section, and slides at the internal freedom of the first breather pipe 52.When using such breather plug, such as dividing plate 7 arrange given prominence to by the surface of the bottom of dividing plate 7 flange portion 54, breather plug extended to connect with the dividing plate 7 at two ends and to be placed in flange portion 54, to 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 such as by fixed axis, be located at its one end wheel and there is flexual sheet metal form, described sheet metal is arranged at its other end with the orthogonal direction, direction that extends relative to fixed axis.If inserted by the passage below breather plug by steady pin 55, then removed by the flexure of sheet metal after passage by sheet metal flexure during passage, steady pin 55 is formed as the state hung from above from breather plug.In addition, by the wheel of tractive steady pin 55, sheet metal by passage, being extracted steady pin 55 thus, further by making the second breather pipe 53 slide, can be unloaded above-mentioned breather plug from the below of heat transfer plate while flexure.
Or, for the breather plug of other form above-mentioned, can enumerate the breather plug had the first breather pipe 52, second breather pipe 53 and afterburning parts 56 as shown in figure 40, described afterburning parts 56 are to by the such parts of the helical spring of the outstanding direction reinforcing of the first breather pipe 52 to the second breather pipe 53.This breather plug is also arranged at the bottom of each section by the dividing plate 7 with flange portion 54.The reinforcing resisting afterburning parts 56 makes breather plug retract and make this breather plug be positioned on flange portion 54, thus this breather plug is arranged at the bottom of each section.In addition, by the reinforcing resisting afterburning parts 56, breather plug is retracted, described breather plug can be unloaded by the below of heat transfer plate.The slip of steady pin 55 and the second breather pipe 53 can by the passage of the bottom by the wheel being hooked on steady pin 55 of instrument shown in Figure 31 or the second breather pipe 53 carries out.
Second manufacture method > of < reaction product
Second manufacture method of reaction product of the present invention uses above-mentioned second plate-type reactor to manufacture the method for reaction product, and the method comprises the operation of the thermal medium body to the desired temperature of above-mentioned heat-transfer pipe supply, also obtains the operation of the reaction product of discharging from above-mentioned gap to the gap supply response raw material between the adjacent heat transfer being filled with catalyst.In the second approach, above-mentioned reaction raw materials is ethene; Be selected from by carbon number be 3 and 4 hydrocarbon and the group that forms of the tert-butyl alcohol at least one or at least one in the group that forms of unsaturated aliphatic aldehyde that to be selected from by carbon number be 3 and 4; Carbon number is the hydrocarbon of more than 4; Dimethylbenzene and/or naphthalene; Alkene; Carbonyls; Cumene hydroperoxide; Butylene; Or ethylbenzene, above-mentioned reaction product is ethylene oxide; Carbon number be 3 and 4 unsaturated aliphatic aldehyde and/or carbon number be the unrighted acid of 3 and 4; 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, is particularly applicable to occur due to high reaction heat the reaction process that catalyst degradation or reaction achievement can reduce in such reaction process.Particularly the second plate-type reactor can be applicable to the reaction raw materials of the fluid that gas or liquid etc. can circulate in the catalyst layer being filled with catalyst, but compared with the situation of liquid condition, more can compatibly for being difficult to the gas of heat extraction when.
Such as, the reaction of the second plate-type reactor is effectively suitable for for following reaction: above-mentioned raw materials is ethene; Be selected from by carbon number be 3 and 4 hydrocarbon and the group that forms of the tert-butyl alcohol at least one or at least one in the group that forms of unsaturated aliphatic aldehyde that to be selected from by carbon number be 3 and 4; The carbon number such as normal butane or benzene is the hydrocarbon of more than 4; Dimethylbenzene and/or naphthalene; Alkene; Carbonyls; Cumene hydroperoxide; Butylene; Or ethylbenzene, the above-mentioned reaction product obtained is ethylene oxide; Carbon number be 3 and 4 unsaturated aliphatic aldehyde and/or carbon number be the unrighted acid of 3 and 4; Maleic acid; Phthalic acid; Alkane; Alcohol; Acetone and phenol; Butadiene; Or styrene.
Particularly preferably be, the second plate-type reactor be applicable to known be easy to produce heat spot, gas phase contact oxidation reaction.Can enumerate reaction raw materials be selected from by carbon number be 3 and 4 hydrocarbon and the group that forms of the tert-butyl alcohol at least one of reaction raw materials or the reaction of at least one of reaction raw materials in the group that forms for unsaturated aliphatic aldehyde that to be selected from by carbon number be 3 and 4.
Specifically, be the hydrocarbon of 3 as above-mentioned carbon number, propylene, propane can be enumerated.Be the hydrocarbon of 4 as above-mentioned carbon number, isobutene, butylene class, butanes can be enumerated.In addition, be the unsaturated aliphatic aldehyde of 3 and 4 as above-mentioned carbon number, methacrylaldehyde, MAL can be enumerated, be the unrighted acid of 3 and 4 as carbon number, acrylic acid, methacrylic acid can be enumerated.
In the second manufacture method of reaction product, can utilize in the catalyst using well-known catalysts used in the existing haptoreaction of above-mentioned reaction raw materials, such as, use the haptoreaction of the above-mentioned reaction raw materials of multi-tubular reactor.May be combined in catalyst in above-mentioned haptoreaction and not there is the inert particles such as reactive mullite ball.In addition, in the second manufacture method of reaction product, for the temperature of thermal medium body being supplied to heat-transfer pipe, such as can with existing haptoreaction, such as use multi-tubular reactor above-mentioned reaction raw materials haptoreaction in reaction condition for benchmark, tried to achieve by the optimization of the reaction condition in the reaction of use second plate-type reactor.Further, for other reaction condition in the second manufacture method of reaction product, such as can by utilizing the optimization of known technology to try to achieve in the same manner as the temperature of above-mentioned thermal medium body.Or, for the reaction condition in the second manufacture method of reaction product, the reaction condition of the first manufacture method of above-mentioned reaction product or the 3rd manufacture method of aftermentioned reaction product can be suitable for.
3rd manufacture method > of < reaction product
3rd manufacture method of reaction product is (A) method or (B) method: (A) to supply response raw mixture in the plate-type reactor possessing the catalyst layer be formed between heat transfer plate, this reacting material mixture contain be selected from by carbon number be 3 and 4 hydrocarbon and the group that forms of the tert-butyl alcohol in reaction raw materials at least one and containing molecularity oxygen; Catalytic gas phase oxidation is carried out to above-mentioned reaction raw materials, at least one reaction product in the group that the unsaturated aliphatic aldehyde that it is 3 and 4 that manufacture is selected from by unsaturated hydrocarbons and carbon number forms.(B) to supply response raw mixture in the plate-type reactor possessing the catalyst layer be formed between heat transfer plate, this reacting material mixture contains at least one and the molecularity oxygen of the reaction raw materials in the group that unsaturated aliphatic aldehyde that to be selected from by carbon number be 3 and 4 forms; Catalytic gas phase oxidation is carried out to above-mentioned reaction raw materials, at least one reaction product in the group that the unrighted acid that it is 3 and 4 that manufacture is selected from by carbon number forms.
Further, in the 3rd manufacture method of reaction product, above-mentioned plate-type reactor is split into more than 2 different conversion zones of the average layer thickness of catalyst layer, the thermal medium body of temperature adjustment is independently carried out to above-mentioned more than 2 conversion zones supply, across above-mentioned heat transfer plate, heat extraction is carried out to the heat generated by above-mentioned oxidation, and independently controls the temperature in above-mentioned catalyst layer.
Further, in the 3rd manufacture method of reaction product, the temperature T (S1) being supplied to the above-mentioned thermal medium body of conversion zone S1 is higher than the temperature T (S2) of above-mentioned thermal medium body being supplied to conversion zone S2, described conversion zone S1 is closest to the entrance of above-mentioned reacting material mixture, 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, to above-mentioned be selected from by carbon number be 3 and 4 hydrocarbon and the group that forms of the tert-butyl alcohol at least one of reaction raw materials be oxidized time, the load of above-mentioned reaction raw materials is more than 150 liter per hour [converting through standard state (temperature 0 DEG C, 101.325kPa)] relative to every 1 liter of catalyst; The load when at least one of the reaction raw materials in the group form the above-mentioned unsaturated aliphatic aldehyde that to be selected from by carbon number be 3 and 4 is oxidized, above-mentioned reaction raw materials is more than 160 liter per hour [converting through standard state (temperature 0 DEG C, 101.325kPa)] relative to every 1 liter of catalyst.
In 3rd manufacture method of reaction product reaction raw materials used be selected from by carbon number be 3 and 4 hydrocarbon and the group that forms of the tert-butyl alcohol at least one of reaction raw materials or at least one of reaction raw materials in the group that forms of unsaturated aliphatic aldehyde that to be selected from by carbon number be 3 and 4.Be the hydrocarbon of 3 as above-mentioned carbon number, propylene, propane can be enumerated.Be the hydrocarbon of 4 as above-mentioned carbon number, isobutene, n-butene, isobutene, normal butane, iso-butane can be enumerated.As the unsaturated aliphatic aldehyde that above-mentioned carbon number is 3 and 4, methacrylaldehyde, MAL can be enumerated.
Just be not particularly limited as long as the state of these reaction raw materials has the mobility circulated in above-mentioned catalyst layer, preferred exemplary can go out state for gas (reaction raw materials gas).
In addition, as the unsaturated hydrocarbons of above-mentioned reaction product, carbon number be 3 and 4 unsaturated aliphatic aldehyde and carbon number be in the unrighted acid of 3 and 4, as unsaturated hydrocarbons, can butadiene be enumerated; As the unsaturated aliphatic aldehyde that carbon number is 3 and 4, methacrylaldehyde, MAL can be enumerated; As the unrighted acid that carbon number is 3 and 4, acrylic acid, methacrylic acid, maleic acid, maleic anhydride can be enumerated.
Herein, think that the reason that the 3rd manufacture method of reaction product can be suitable at above-mentioned total overall reaction product is as follows.
As above-mentioned reason, can enumerate such as, the propylene being 3 by carbon number manufactures methacrylaldehyde, be that the isobutene of 4 manufactures MAL and manufacture the basic composition (such as molybdenum (Mo)-bismuth (Bi) is) of butadiene catalyst used, method for making and shape by n-butene substantially identical by carbon number, and reaction formation in the manufacture of this reaction product, operation are industrially identical.Can enumerate further, manufacture acrylic acid by the methacrylaldehyde as unsaturated aliphatic aldehyde, manufactured methacrylic acid by MAL and also use same basic composition (such as molybdenum (Mo)-vanadium (V) is), the catalyst of shape by butylene class manufacture maleic anhydride, utilize identical reaction formation, operation to carry out industrial reaction manufacture.These reactions are the catalytic gas phase oxidation utilizing molecularity oxygen, and are the reactions being attended by larger heat release, and according to the opinion of the present inventor, these reactions have same response characteristic, and therefore thinking can the 3rd manufacture method of effective application response product.
The above-mentioned reacting material mixture being supplied to above-mentioned plate-type reactor contains reaction raw materials, molecularity oxygen and contains the gas that nitrogen, steam etc. are inertia to reaction as required.Above-mentioned reaction raw materials can be the formation of only a kind, and the mixture (such as mist) that also can mix for two or more.The composition of above-mentioned reacting material mixture (such as reaction mixture gas body) is suitably selected according to object.
Above-mentioned reaction raw materials is not particularly limited relative to the content of above-mentioned reacting material mixture, as the total amount of reaction raw materials, is preferably 5 ~ 13 % by mole.In addition, above-mentioned molecularity oxygen is preferably 1 ~ 3 times amount of reaction raw materials total amount relative to the content of above-mentioned reacting material mixture.
The gas of above-mentioned inertia is from above-mentioned reacting material mixture total amount, deduct the total amount of reaction raw materials and the value of molecularity oxygen amount relative to the content of above-mentioned reacting material mixture.In addition, the gas of above-mentioned inertia can use the inert gas recycled the tail gas of being discharged by reaction system.
In the 3rd manufacture method of reaction product, known catalyst can be used according to object.As the composition of catalyst, the metal oxide containing molybdenum, tungsten, bismuth etc. or the metal oxide containing vanadium etc. can be enumerated.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, can suitably use diameter to be the spherical of 1 ~ 15mm (millimeter); Or the shape beyond ellipse, the equivalent diameter with 1 ~ 15mm granular; Or the ring-type of cylindrical center's perforate of cylinder shape, circle external diameter is 4 ~ 10mm, circle internal diameter is 1 ~ 3mm, be highly the shape of 2 ~ 10mm.More preferably above-mentioned diameter, equivalent diameter, circle external diameter and be highly the catalyst of 3 ~ 5mm.
When reaction raw materials is propylene, as above-mentioned metal oxide, the compound shown in following general formula (1) suitably can be exemplified.
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 above-mentioned formula (1), Mo represents molybdenum; Bi represents bismuth; Co represents cobalt; Ni represents nickel; Fe represents iron; X represents at least one element in the group being selected from sodium, potassium, rubidium, caesium and thallium composition; Y represents at least one element in the group being selected from and being made up of boron, phosphorus, arsenic and tungsten; Z represents at least one element in the group being selected from and being made up of magnesium, calcium, zinc, cerium and samarium; Q represents halogens; Si represents silicon; 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, when molybdenum atom (Mo) is 12,0.5≤b≤7,0≤c≤10,0≤d≤10,1≤c+d≤10,0.05≤e≤3,0.0005≤f≤3,0≤g≤3,0≤h≤1,0≤i≤0.5,0≤j≤40, k is the value determined by the state of oxidation of each element.
On the other hand, when reaction raw materials is methacrylaldehyde, as above-mentioned metal oxide, the compound shown in following general formula (2) suitably can be exemplified.
Mo (12) V (a) X (b) Cu (c) Y (d) Sb (e) Z (f) Si (g) C (h) O (i) formula (2)
In above-mentioned formula (2), X represents at least one element in the group being selected from and being made up of Nb and W.Y represents at least one element in the group being selected from and being made up of Mg, Ca, Sr, Ba and Zn.Z represents at least one element in the group being selected from and 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 the atomic ratio of each element, be 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 relative to molybdenum atom (Mo); I is the value determined by the oxidizability of each composition among above-mentioned each composition except C.
In the reactor of practicality, require the processing load amount of the reaction raw materials improving unit catalyst, to increase the productivity ratio of goal response product.But, when the processing load amount of the reaction raw materials of raising unit catalyst, need to be used for suitably controlling to prevent heat spot by the heat of reaction generation, prevent the damage of catalyst and the scheme of the raising conversion ratio of reaction raw materials and the yield of goal response product.
In order to corresponding, for the plate-type reactor of the 3rd manufacture method for reaction product, its shape etc. is not particularly limited, but with following (1) and (2) for feature.
(1) more than 2 conversion zones that the average layer thickness of the catalyst layer formed between heat transfer plate is different are divided into.
(2) to the thermal medium body that more than 2 conversion zone supplies adjust through temperature, the thermal medium body adjusted through temperature is independently supplied with upper curtate if desired to 2, the heat generated by catalytic gas phase oxidation reaction is carried out heat extraction across heat transfer plate, thus can temperature in independent catalyst layer.
As such plate-type reactor, the plate-type reactor of the invention described above can be utilized.In the 3rd manufacture method of reaction product, from the viewpoint of the effect of both effects of the 3rd manufacture method of the effect and reaction product that obtain plate-type reactor of the present invention, preferably in third method, use plate-type reactor of the present invention.
Describe the embodiment of the above-mentioned plate-type reactor of the 3rd manufacture method for reaction product below.It should be noted that, in record below, in order to easy, " reacting gas " of one of mode using reacting fluid general name of the mixture etc. of reaction product of reaction raw materials, reacting material mixture being described and being generated by reaction sometimes.
As the 1st mode of plate-type reactor, catalyst filling in the space clamped by a pair heat transfer plate can be enumerated and come forming reactions region, there is the plate-type reactor of the thermal medium body stream of the outside supply thermal medium body to heat transfer plate.
The conversion zone of above-mentioned plate-type reactor can be divided into 2 with upper curtate, can be changed the catalyst layer thickness of filling in each conversion zone by the interval adjusting a pair heat transfer plate.The structure that the catalyst layer thickness being everywhere particularly preferably conversion zone increases from the entrance of supplied reacting material mixture towards outlet.In addition, outside right for heat transfer plate can be divided into the thermal medium body stream of more than 2, there is to the supply of this stream the thermal medium body of different temperature.
Flow along heat transfer plate in the direction being supplied to the reacting gas of above-mentioned plate-type reactor, thermal medium body supplies to the outside of a pair heat transfer plate.The flow direction of this thermal medium body is not particularly limited, but usually needs to hold a large amount of catalyst, arrange multiple heat transfer plate pair in plant-scale reaction unit, is thus more suitably with the direction at a right angle that flows to of reacting gas.
Reacting dose in usual reaction is maximum at the intake section of reacting gas, and the generation along with the reaction heat of reaction is maximum, then reduces at the Way out of reacting gas.The average layer thickness being changed catalyst layer by the interval adjusting heat transfer plate can more critically control to react and by reacting the heat produced, can prevent the generation of the heat spot of the rising along with catalyst layer temperature, and can prevent the damage of catalyst.
In addition, by using above-mentioned plate-type reactor, can eliminate seen in multi-tubular reactor to, under the condition that the processing load amount of the unit catalyst of reacting gas is high, the increase of the pressure loss of reacting gas and the reduction of the yield of goal response product of accompanying with it.Further, the cost of energy of supply compressor that accompany with the rising of pressing in reactor, reacting gas etc. can be cut down.
Figure 41 shows the 1st concrete example of above-mentioned plate-type reactor.
The thin plate heat transfer plate (57) of thermal medium body stream (60-1,60-2 and 60-3) and catalyst layer (43) being kept apart deforms to change the thickness of catalyst layer (43) along from reaction gas inlet (58) to the flow direction exporting (59).Herein, the average layer thickness of catalyst layer is the distance between the plate that records in the direction that the flow direction of reacting gas is rectangular.
The thickness being formed at the catalyst layer (43) between a pair heat transfer plate (57) corresponds to each thermal medium body stream (60-1,60-2 and 60-3) and forms each conversion zone (S1, S2 and S3).(61) be thermal medium body supply port.It should be noted that, in above-mentioned, conversion zone is set to 3, but this is example, the number of conversion zone indefinite.
In addition, in heat transfer plate (57), flat board can be used, process with the ripple plate making it have concavo-convex buckplate or be shaped through the direction rectangular with the flow direction of reacting gas through embossing.If consider the heat transfer efficiency between reacting gas and thermal medium body, be then suitable for using buckplate or ripple plate shape.Herein, in the 1st concrete example, use in the heat transfer plate (57) average layer thickness of catalyst layer when embossing processing or ripple plate with as shown in the formula regulation.
(formula) [average layer thickness of catalyst layer]=[volume of catalyst layer] ÷ [length (wide) (length perpendicular to the direction of paper in Figure 41) of heat transfer plate] ÷ [length of the flow direction of the reacting gas of heat transfer plate]
Herein, [volume of catalyst layer] is as follows: make a pair heat transfer plate of formation catalyst layer keep vertical relative to ground, and lid is set in bottom (bottom of each conversion zone), and in the space clamped by a pair heat transfer plate, inject the bead of the liquid such as water or below diameter 1mm, now, be full of the volume of the bead of the liquid such as the water required for this space or below diameter 1mm, be the volume of catalyst layer.
As the second method of above-mentioned plate-type reactor, following plate-type reactor can be enumerated: namely, in described plate-type reactor, making by figuration is be the continuous pattern of main constitutive requirements with circular arc, elliptic arc, rectangle or a polygonal part ripple plate 2 is relative, and the thermal medium body stream of formation more than 2 that the convex surface part of this two ripples plate is bonded with each other, obtain heat transfer plate, make the multiple arrangement of obtained heat transfer plate and make the ripple plate convex surface part of adjacent heat transfer plate relative with concave part, forming the catalyst layer of appointed interval.Herein, above-mentioned what is called " be by figuration be the continuous pattern of main constitutive requirements with circular arc, elliptic arc, rectangle or a polygonal part ripple plate " means that the shape of the ripple of ripple plate is the continuous pattern (shape) that is main constitutive requirements with circular arc, elliptic arc, rectangle or a polygonal part.
In above-mentioned plate-type reactor, being the shape of the circular arc of ripple plate, elliptic arc, rectangle or a polygonal part by changing by figuration, the thickness of catalyst layer can be changed by the entrance of reacting gas being supplied to catalyst layer to exit.In addition, in above-mentioned plate-type reactor, conversion zone can be split into the field of more than 2, and the conversion zone being split into more than 2 fields can be made corresponding with the varied in thickness of above-mentioned catalyst layer.Further, in more than 2 conversion zones after segmentation, independent supply, through the thermal medium body of temperature adjustment, carries out heat extraction to the heat generated by catalytic gas phase oxidation reaction across heat transfer plate, can temperature in independent catalyst layer.
Be supplied to the flows outside of direction along heat transfer plate of the reacting gas of above-mentioned plate-type reactor, thermal medium body is supplied to the inner side of a pair heat transfer plate.The flow direction of this thermal medium body is right angle orientation relative to the flowing of reacting gas, namely flows with the direction of cross flow.
Reacting dose in usual reaction is maximum at the intake section of reacting gas, and with reacting, the reaction heat produced is maximum, reduces at the Way out of reacting gas.In order to effectively carry out the heat extraction of this reaction heat, the concaveconvex shape of the ripple plate that preferred change one heat transfer plate and adjacent heat transfer use, the gap adjusting two heat transfer plates makes the average layer thickness of catalyst layer change.By changing the average layer thickness of catalyst layer, more critically can control reaction, along with the rising of catalyst layer temperature, 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), the continuous pattern that to be deformed into by 2 thin plates with circular, oval, rectangle or a polygonal part be 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, the distance ground of the half being equivalent to thermal medium body stream that a pair heat transfer plate (57) offset one from another is relative, forms gap, to formed gap-fill catalyst, forms catalyst layer (43).Further, a pair heat transfer plate (57) has and imports the reaction gas inlet (58) of reaction mixture gas body and the reaction gas outlet (59) of derivation reacting gas to catalyst layer (43).
In above-mentioned thermal medium body stream, the cross sectional shape (sectional area) of each stream is different, and the width of thermal medium body stream (60-1) is maximum.When the width of thermal medium body stream (60-1) is maximum, the alternate constant of adjacent above-mentioned heat transfer plate (57), thus the ripple plate convex surface part of adjacent heat transfer and concave part opposite face and the interval (A) (i.e. the thickness of catalyst layer (43)) formed is the narrowest.By thermal medium body stream (60-2) thermotropism dielectric stream (60-3), the width of thermal medium body stream reduces successively, and the thickness of the catalyst layer (43) corresponding with this thermal medium body stream increases.Thus, in the catalyst layer (43) corresponding with thermal medium body stream (60-1,60-2 and 60-3), the average layer thickness of each catalyst layer is different, can form more than 2 conversion zones (S1, S2 and S3) that the average layer thickness of catalyst layer is different.
Herein, the average layer thickness of catalyst layer refer in each catalyst layer of each conversion zone (S1, S2 and S3) and the rectangular direction of the flow direction of reacting gas on the mean value at above-mentioned interval (A) that measures.In the 2nd concrete example, calculating formula shown below is used to specify.
(formula) [average layer thickness of catalyst layer]=[volume of catalyst layer] ÷ [length (wide) (length perpendicular to the direction of paper in Figure 42) of heat transfer plate] ÷ [length of the flow direction of the reacting gas of heat transfer plate]
Herein, [volume of catalyst layer] is as lower volume: keep vertical making a pair heat transfer plate of formation catalyst layer relative to ground, and lid is set in bottom (bottom of each conversion zone), the bead of the liquid such as water or below diameter 1mm is injected in the space clamped by a pair heat transfer plate, now, the volume of the bead of the liquid such as the water required for this space or below diameter 1mm is full of.
It should be noted that, hereinbefore, conversion zone is decided to be 3, but this is only example, the number of conversion zone in the 3rd manufacture method of reaction product indefinite.
Based on Figure 43, the formation of the heat transfer plate (57) used in the 2nd concrete example of above-mentioned plate-type reactor is described in more detail.Figure 43 shows following heat transfer plate: relative by being deformed into the ripple plate 2 of circular arc, elliptic arc, rectangle or the polygonal part continuous print pattern that is main constitutive requirements, and be bonded with each other by the protuberance of this two ripples plate, thus form the thermal medium body stream of more than 2.
The size of thermal medium body stream and the average layer thickness of catalyst layer specify with (L) and wave height (H) that are equivalent to the period of wave of ripple plate.Now, be preferably 10 ~ 100mm period of wave (L), be more preferably 20 ~ 50mm.On the other hand, highly (H) is preferably 5 ~ 50mm, is more preferably 10 ~ 30mm.
This heat transfer plate is pair of parallel heat transfer plate, and the distance (L/2) of the half being equivalent to thermal medium body stream that offsets one from another relative, formed gap, to this gap-fill catalyst, formed catalyst layer.
Regulated by cycle (L) at the interval (P) Yu thermal medium body stream that change this pair parallel heat transfer plate and height (H) thickness to catalyst layer.The interval P of a pair heat transfer plate is generally 10 ~ 50mm, is more preferably 20 ~ 50mm.
In Figure 43, the shape of heat transfer plate is depicted with a part for circular arc, the continuous pattern that this shape also can be is main constitutive requirements with elliptic arc, rectangle, triangle or a polygonal part.By change the above-mentioned cycle (L) and height (H) can precision catalyst layer thickness well.In addition, catalyst layer thickness is preferably homogeneous on the length of heat transfer plate (width) direction (direction vertical with paper).
In addition, the interval (x) shown in the average layer thickness of above-mentioned catalyst layer and Figure 43 is relevant, and this interval (x) is generally 0.7 ~ 0.9 times of the average layer thickness of the catalyst layer that above-mentioned formula specifies.
The thin plate of the heat transfer plate (57) of each reactor uses thickness of slab to be below 2mm, to be suitably the steel plate of below 1mm.
The length in the reactant gas flow direction of heat transfer plate (57) is 0.5 ~ 10m (rice), is preferably 0.5 ~ 5m, more preferably 0.5 ~ 3m.According to can the size of the conventional thin plate steel plate obtained, when described length is more than 1.5m, also 2 plates can be engaged or combinationally use.
The length in the direction (degree of depth among Figure 41 and 42 with paper perpendicular direction) rectangular with the flow direction of reacting gas is not particularly limited, and usually uses 0.1 ~ 20m, preferably uses 3 ~ 15m.Be more preferably 6 ~ 10m.Heat transfer plate (57) lamination in the same manner as the configuration shown in Figure 43, the sheet number of lamination does not limit.In practice, the catalytic amount required for reaction is determined, and is 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 shape (particle diameter etc.) of the load of reaction raw materials and catalyst, in the plate-type reactor shown in Figure 41, can the preferred exemplary average layer thickness that goes out the catalyst layer of conversion zone (S1) be 4 ~ 18mm (being more preferably 5 ~ 13mm), the average layer thickness of the catalyst layer of the conversion zone (S2) after this conversion zone (S1) is 5 ~ 23mm (being 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 (being more preferably 10 ~ 22mm).
On the other hand, in the plate-type reactor shown in Figure 42, can the preferred exemplary average layer thickness that goes out the catalyst layer of conversion zone (S1) be 5 ~ 20mm (being more preferably 7 ~ 15mm), the average layer thickness of the catalyst layer of conversion zone (S2) after this conversion zone (S1) is 7 ~ 25mm (being more preferably 10 ~ 20mm), the average layer thickness of the catalyst layer of conversion zone (S3) after this conversion zone (S2) is 12 ~ 30mm (being more preferably 15 ~ 25mm).
In addition, the average layer thickness of the catalyst layer of these more than 2 conversion zones preferably increases successively according to the position from the entrance of reacting gas to the direction of outlet.
Particularly to be selected from by carbon number be 3 and 4 hydrocarbon and the group that forms of the tert-butyl alcohol at least one of reaction raw materials be oxidized time, the load of reaction raw materials relative to every 1 liter of catalyst be 150 liter per hour [through standard state (temperature 0 DEG C, 101.325kPa) convert] more than when, and/or when being oxidized at least one of the reaction raw materials be selected from by carbon number in the group that forms of unsaturated aliphatic aldehyde being 3 and 4, the load of reaction raw materials relative to every 1 liter of catalyst be 160 liter per hour [through standard state (temperature 0 DEG C, 101.325kPa) convert] more than when, the average layer thickness of the catalyst layer of the conversion zone (S1) be connected with the reaction gas inlet (58) importing reaction mixture gas body to above-mentioned catalyst layer (43) is 5 ~ 15mm (being particularly preferably 7 ~ 12mm), the average layer thickness of the catalyst layer of the conversion zone (S2) more preferably after this conversion zone (S1) is 7 ~ 17mm (being particularly preferably 10 ~ 15mm), the average layer thickness of the catalyst layer of the conversion zone (S3) after this conversion zone (S2) is 12 ~ 27mm (being particularly preferably 15 ~ 20mm).
When the average layer thickness of above-mentioned catalyst layer is less than above-mentioned scope, during to above-mentioned conversion zone S1 catalyst filling, there is bridge joint (Block リ ッ ジ) in catalyst granules in catalyst layer, and be attended by filling time elongated difficulty such as grade.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.Thus, the average layer thickness of the catalyst layer of above-mentioned example is suitable when the particle diameter of catalyst granules is 3 ~ 5mm.
On the other hand, when the average layer thickness of catalyst layer is greater than above-mentioned scope, easily become the reason producing heat spot.If the temperature in the catalyst layer of the conversion zone (such as conversion zone (S3)) near the outlet particularly occurring reacting gas rises, produce the situation of heat spot phenomenon, or there is the conversion ratio of reaction raw materials too high situation close to heat spot like this compared with optimum value, then may occur reacting the phenomenon that achievement reduces, the yield of goal response product reduces.When above-mentioned condition deterioration, generation heat spot, also there will be catalyst damage.Now, need to reduce the temperature limiting reacting dose of thermal medium body and promote the removing of reaction heat, or reduce the quantity delivered of reaction mixture gas body and reduce the load of reaction raw materials.
The details of the average layer thickness of above-mentioned catalyst layer is different according to the change of reacting dose, and the entrance of self-catalysis oxidant layer (43) to outlet can consecutive variations, also can stepsly change.When manufacturing catalyst if consider, reactivity is inconsistent, and the average layer thickness changing above-mentioned catalyst layer can guarantee the free degree then stepsly.
In addition, the Segmentation Number of above-mentioned conversion zone is preferably 2 ~ 5, preferably by the entrance of reacting gas towards outlet, the average layer thickness of the catalyst layer of each conversion zone increases.
Further, for the length of the flow direction of the reacting gas of the catalyst layer in each conversion zone, consider that the conversion ratio etc. of reaction raw materials is determined, such as, when above-mentioned conversion zone is divided into 3, preferred use relative to whole catalyst layer length, conversion zone (S1) part be 10% ~ 55%, conversion zone (S2) part be 20% ~ 65%, conversion zone (S3) part be 25% ~ 70% catalyst layer length.In addition, the catalyst layer length of conversion zone (S3) part preferably changes according to the fulfilling rate of the conversion ratio of reaction raw materials.
As mentioned above, in the reactor of practicality, when the processing load amount of the reaction raw materials of unit catalyst is improved, also the heat suitably controlling to be generated by reaction is needed, 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, to be selected from by carbon number be 3 and 4 hydrocarbon and the group that forms of the tert-butyl alcohol at least one of reaction raw materials be oxidized time, the load of reaction raw materials is more than 150 liter per hour [converting through standard state (temperature 0 DEG C, 101.325kPa)] relative to every 1 liter of catalyst.To above-mentioned be selected from by carbon number be 3 and 4 hydrocarbon and the group that forms of the tert-butyl alcohol at least one of reaction raw materials be oxidized time, the load of reaction raw materials is preferably 170 ~ 290 liter per hour [converting through standard state (temperature 0 DEG C, 101.325kPa)] relative to every 1 liter of catalyst, is particularly preferably 200 ~ 250 liter per hour [converting through standard state (temperature 0 DEG C, 101.325kPa)] relative to every 1 liter of catalyst.The load of above-mentioned reaction raw materials is that more than 150 liter per hour [converting through standard state (temperature 0 DEG C, 101.325kPa)] mean the state that the processing load amount of the reaction raw materials of above-mentioned unit catalyst is improved relative to every 1 liter of catalyst.
In addition, the load when at least one of the reaction raw materials in the group formed the unsaturated aliphatic aldehyde that to be selected from by carbon number be 3 and 4 is oxidized, reaction raw materials is more than 160 liter per hour [converting through standard state (temperature 0 DEG C, 101.325kPa)] relative to every 1 liter of catalyst.The load when at least one of the reaction raw materials in the group form the above-mentioned unsaturated aliphatic aldehyde that to be selected from by carbon number be 3 and 4 is oxidized, reaction raw materials is preferably 180 ~ 300 liter per hour [converting through standard state (temperature 0 DEG C, 101.325kPa)] relative to every 1 liter of catalyst, is particularly preferably 200 ~ 250 liter per hour [converting through standard state (temperature 0 DEG C, 101.325kPa)] relative to every 1 liter of catalyst.The load of above-mentioned reaction raw materials is that more than 160 liter per hour [converting through standard state (temperature 0 DEG C, 101.325kPa)] mean the state that the processing load amount of the reaction raw materials of above-mentioned unit catalyst is improved relative to every 1 liter of catalyst.
In the 3rd manufacture method of reaction product, in order to the yield of the conversion ratio and goal response product that improve reaction raw materials, independent control is carried out to the thermal medium temperature being supplied to more than 2 conversion zones.In addition, in the 3rd manufacture method of reaction product, the unit of temperature is degree Celsius [DEG C].
In the 3rd manufacture method of reaction product, in order to the yield of the conversion ratio and goal response product that improve reaction raw materials, the temperature T (S1) being supplied to the thermal medium body of the conversion zone S1 of the entrance closest to reacting material mixture is higher than being supplied to adjacent with conversion zone S1 and the temperature T (S2) being positioned at the thermal medium body of the conversion zone S2 in the downstream of reacting material mixture stream is important.
In addition, " T (S1)-T (S2) " is more preferably more than 5 DEG C, more preferably more than 10 DEG C, is particularly preferably more than 15 DEG C.In addition, " T (S1)-T (S2) " is preferably less than 40 DEG C.
In addition, be supplied to above-mentioned conversion zone S2, to be positioned at the temperature that reacting material mixture flows down the thermal medium body of the conversion zone of trip be arbitrary, can be identical with temperature T (S2), also can be different.But, be particularly in the conversion zone of the scope of more than 90% at the conversion ratio comprising reaction raw materials, preferably lower than the temperature of temperature T (S2).
In the example of the plate-type reactor described in above-mentioned Figure 41 and 42, the temperature T (S1) being supplied to the thermal medium body of conversion zone (S1), higher than when being supplied to temperature T (S2) of thermal medium body of conversion zone (S2), can improve the conversion ratio of reaction raw materials and the yield of goal response product.
In addition, in order to improve the yield of goal response product further, the temperature being preferably supplied to the thermal medium body of the conversion zone of the outlet closest to reacting material mixture is lower than being supplied to adjacent with this conversion zone and being positioned at the temperature of the thermal medium body of the conversion zone of the upstream of reacting material mixture stream.In addition, more preferably the absolute value of this temperature difference is more than 5 DEG C, is particularly preferably more than 10 DEG C.In addition, the absolute value of this temperature difference is preferably less than 30 DEG C.
In the 3rd manufacture method of reaction product, when the temperature being supplied to the specific thermal medium body of conversion zone S (j) is arbitrarily set to T (Sj), will be supplied to adjacent with above-mentioned conversion zone S (j) and the temperature being positioned at the thermal medium body of the conversion zone S (j+1) in the downstream of reacting material mixture stream is set to T (Sj+1) time, more preferably above-mentioned T (Sj) and above-mentioned T (Sj+1) meets the relation of T (Sj) >T (Sj+1).
In the example of the plate-type reactor described in above-mentioned Figure 41 and Figure 42, when the temperature of the thermal medium body being supplied to conversion zone (S1) being set to T (S1), the temperature of the thermal medium body being supplied to conversion zone (S2) being set to T (S2), when the temperature of the thermal medium body being supplied to conversion zone (S3) is set to T (S3), preferably meeting the relation of T (S1) >T (S2) >T (S3).
In the 3rd manufacture method of reaction product, in order to improve the yield of goal response product further, more preferably the temperature being supplied to the specific thermal medium body of conversion zone S (j) is arbitrarily set to T (Sj), will be supplied to adjacent with above-mentioned conversion zone S (j) and the temperature being positioned at the above-mentioned thermal medium body of the conversion zone S (j+1) in the downstream of reacting material mixture stream is set to T (Sj+1) time, above-mentioned T (Sj) and above-mentioned T (Sj+1) meets T (Sj)-T (relation of Sj+1)≤5.In addition, further preferably T (Sj)-T (Sj+1)≤10, particularly preferably T (Sj)-T (Sj+1)≤15.In addition, the value of T (Sj)-T (Sj+1) is preferably less than 30.
As mentioned above, for the conversion ratio of reaction raw materials is remained on the best, the temperature of thermal medium body is regulated.In the 3rd manufacture method of reaction product, when for promoting the carrying out of reaction to scheme the raising of reaction raw materials conversion ratio, improve be supplied to the thermal medium body of the conversion zone of the upstream of the flow direction being positioned at reacting material mixture temperature to regulate reaction.Otherwise when hope reduces too high conversion ratio, first reduction is supplied to the temperature of the thermal medium body of the conversion zone in the downstream of the flow direction being positioned at reacting material mixture to regulate 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, be more preferably more than 95%, be particularly preferably more than 97%.
Thermal medium body is supplied in more than 2 conversion zones with optimum temperature respectively.Now, the direction making thermal medium body flow is preferably orthogonal with the flow direction of reacting gas.
In addition, the inlet temperature of thermal medium body and the temperature difference of outlet temperature are preferably 0.5 ~ 10 DEG C, are more preferably 2 ~ 5 DEG C.
When the plate-type reactor shown in Figure 42, in each thermal medium body stream (60-1,60-2,60-3), also can change the flow of thermal medium body, temperature and flow direction by every more than 1 ~ 2 stream.In addition, in a conversion zone, the situation that every more than 1 ~ 2 stream makes the thermal medium body of identical temperature flow with equidirectional independently is also had, situation about flowing in the opposite direction in addition.In addition, the thermal medium body that the thermal medium body stream that also may be supplied to certain conversion zone is also discharged is supplied in the thermal medium body stream of identical or other conversion zone.
Also more reliably independent control is carried out to the temperature in the catalyst layer in conversion zone to carry out heat extraction to the heat generated by reaction across above-mentioned heat transfer plate, it is very important for carrying out stable control to the temperature of the thermal medium body being supplied to conversion zone, and the temperature of thermal medium body preferably has separately independently temperature control device.Such as, when being back to conversion zone S (j) of upstream by conversion zone S (j+1) thermal medium body out, also preferred after utilizing temperature control device adjustment thermal medium temperature T (Sj), resupply to conversion zone S (j).In addition, also can shunt rear or collaborate the adjustment of laggard trip temperature with from the thermal medium body of other conversion zone or the thermal medium body of different temperatures, being supplied to conversion zone S (j).
The temperature being supplied to the thermal medium body of thermal medium body stream preferably supplies with 200 ~ 600 DEG C.Reaction raw materials be selected from by carbon number be 3 and 4 hydrocarbon and the group that forms of the tert-butyl alcohol at least one of reaction raw materials time, be preferably supplied to each conversion zone with 250 ~ 450 DEG C, be more preferably 300 ~ 420 DEG C.When this reaction raw materials is propylene, the temperature being preferably supplied to the thermal medium body of more than 2 conversion zones is 250 ~ 400 DEG C, is more preferably 320 ~ 400 DEG C.
On the other hand, when reaction raw materials is at least one of reaction raw materials in the group that forms of unsaturated aliphatic aldehyde that to be selected from by carbon number be 3 and 4, is preferably supplied to each conversion zone with 200 ~ 350 DEG C, is more preferably 250 ~ 330 DEG C.When this reaction raw materials is methacrylaldehyde, the temperature being preferably supplied to the thermal medium body of more than 2 conversion zones is 250 ~ 320 DEG C.
In same conversion zone, the temperature of preferred thermal medium body is substantially identical, but can change in the scope not producing heat spot phenomenon.
The flow being supplied to the thermal medium body of thermal medium body stream determined by heat of reaction and heat transfer impedance (Den Hot resists).But, for heat transfer impedance, usually little gas side due to reacting gas the resistance of heat transfer Chinese People's Anti-Japanese Military and Political College in the thermal medium body as liquid heat transfer impedance and have problems, but the liquidus speed in thermal medium body stream suitably adopts more than 0.3m/s.In order to obtain and the value that do not have problems little as the impedance on thermal medium side compared with resisting with 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, not preferred from economic aspect.In addition, the thermal medium body used can use known material.
In the 3rd manufacture method of reaction product, reaction pressure is generally normal pressure ~ 3,000kPa (kPa), is preferably normal pressure ~ 1,000kPa (kPa), is more preferably normal pressure ~ 300kPa.
Embodiment
Use embodiment to be specifically described below, but the present invention is not by any restriction of embodiment.
(embodiment 1)
In first plate-type reactor, heat in catalyst layer is given and accepted and can effectively be carried out, as long as the reaction thus for needing heat to give and accept, all can be suitable for for any raw material, catalyst, reaction, herein show and utilize oxygen to carry out oxidation to manufacture methacrylaldehyde, acrylic acid reaction as embodiment to propylene.
When utilizing molecularity oxygen to carry out oxidation to manufacture methacrylaldehyde to propylene, manufacture catalyst as follows according to the disclosed method such as Japanese Laid-Open Patent Publication 63-54942 publication, Japanese Patent Publication 6-13096 publication, Japanese Patent Publication 6-38918 publication.
(manufacture of catalyst)
By 94 weight portion ammonium paramolybdate heating for dissolving in 400 parts by weight of purified water.In addition by 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 and mixes simultaneously, obtain the solution of pulp-like.
Next, 0.85 weight portion borax and 0.36 parts by weight of potassium nitrate are dissolved in 40 parts by weight of purified water under heating, are added in above-mentioned slurry.Add 64 weight portion pelletized silicas subsequently to stir.Then add the bismuth subcarbonate that 58 weight portions are compounded with 0.8 % by weight Mg to be in advance uniformly mixed, after this slurry heat drying, heat treatment in 1 hour is carried out in air atmosphere in 300 DEG C, obtained granular solids use forming machine is sprayed the lozenge that ingot is shaped to diameter 4mm, height 3mm, next carry out 4 hours fire at 500 DEG C, obtain catalyst A.
The catalyst A obtained is the composite oxides of the ratio of components with 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 determined according to the state of oxidation of each metal).
Use, with the plate-type reactor of Fig. 1, there is the oxidation reaction that the same plate-type reactor A formed carries out propylene.In plate-type reactor A, the corrosion resistant plate that thickness is 1mm is formed, there is the heat transfer plate that formed by plate 2 chip bonding after being shaped, the major diameter (L) of heat-transfer pipe 1 is 40mm, the minor axis (H) of heat-transfer pipe is 20mm, the axle base (P) of heat transfer plate is 26mm, has a conversion zone, accommodates catalyst A.Utilize CCD laser extensometer ((strain) KEYENCE society manufactures LK-G152) to measure the shape of the plate after shaping, the plate after result is shaped is relative to the error deficiency ± 0.2mm of the design load be shaped.In plate-type reactor A, the mode that heat transfer plate is vertical direction according to its axle is configured.
The design load of the distance between the surface of the heat transfer plate in plate-type reactor A with the flange of the heat-transfer pipe based on side's heat transfer plate and based on the connecting portion of the heat-transfer pipe of the opposing party's heat transfer plate recessed edge between distance count 15mm.For above-mentioned heat transfer plate surface between distance, axis along heat transfer plate measures 7 places, measures 3 places along the axis of heat-transfer pipe in heat transfer plate, add up to mensuration 21 place, result is also 17 places at 81% of measuring point, and the difference of above-mentioned design load and measured value is within 0.2mm.In addition, distance between the surface of heat transfer plate is undertaken measuring by inserting the following two kinds mensuration accessory (gold utensil) 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 has at right angles to been installed in the position of 30mm the front end of the pole member by length 50cm, diameter 4mm.For plate-type reactor A, in the distance between the surface of heat transfer plate, the difference of measured value and design load is had to be the situation of 0mm.
Thermal medium uses Nitrates mixture fuse salt (Na イ タ ー).Thermal medium is adjusted to the temperature of applicable conversion zone, is supplied to heat-transfer pipe.Thermal medium is that more than 0.7m per second supplies by the flow velocity of thermal medium.
As unstrpped gas, be 9.5 % by mole by density of propylene, the reaction raw materials mist of water concentration 9.5 % by mole, oxygen concentration 14.2 % by mole, nitrogen 66.8% is supplied to plate-type reactor to make the pressure of reactor inlet for 0.07MPaG (MPa gauge pressure) with the ratio of 6750 liters (standard state) per hour.
Distance (P) between the length of the major diameter of the heat-transfer pipe in plate-type reactor A, minor axis, conversion zone and heat transfer plate is listed in table 1.In addition the peak temperature of the temperature of thermal medium, conversion ratio, selection rate and catalyst layer as raw material propylene (PP) is 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]
[table 2]
(embodiment 2)
Except making the axle base (P) of heat transfer plate for except 26.5mm, using and there is plate-type reactor B isostructural with plate-type reactor A phase, first adopt the condition identical with embodiment 1 to implement to react.The measured value of the distance between surface in plate-type reactor B, heat transfer plate is the distance between the flange of side's heat transfer plate and the recessed edge of the opposing party's heat transfer plate, measure above-mentioned distance similarly to Example 1, result is also 16 places at 76% of measuring point is 15.5 ± 0.2mm.The difference that plate-type reactor B is equivalent to measured value and above-mentioned design load is the situation of+0.5mm.In the reaction, the peak temperature of catalyst layer is 419 DEG C, and increases further, 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 in embodiment 1, the temperature of thermal medium is reduced to 338 DEG C, implement reaction in addition similarly to Example 1, result is as shown in table 2, obtains the reaction achievement equal with embodiment 1.
(embodiment 3)
Except making the axle base (P) of heat transfer plate for except 27.5mm, using and there is plate-type reactor C isostructural with plate-type reactor A phase, first adopt the condition identical with embodiment 1 to implement to react.The measured value of the distance between surface in plate-type reactor C, heat transfer plate is the distance between the flange of side's heat transfer plate and the recessed edge of the opposing party's heat transfer plate, measure above-mentioned distance similarly to Example 1, result is also 18 places at 86% of measuring point is 16.5 ± 0.2mm.The difference that plate-type reactor C is equivalent to measured value and above-mentioned design load is the situation of+1.5mm.In the reaction, the peak temperature of catalyst layer is 442 DEG C, and increases further, therefore stops reaction for the time being.
In order to make the peak temperature of the catalyst layer of plate-type reactor C identical with the peak temperature of the catalyst layer in embodiment 1, the temperature of thermal medium is reduced to 330 DEG C, implement reaction in addition similarly to Example 1, result is as shown in table 2 obtains the reaction achievement equal with embodiment 1.
(comparative example 1)
Except making the axle base (P) of heat transfer plate for except 28.5mm, using, with plate-type reactor A, there is mutually isostructural plate-type reactor D, first adopt condition similarly to Example 3 to implement reaction.In plate-type reactor D, the measured value of the distance between the surface of heat transfer plate is the distance between the flange of side's heat transfer plate and the recessed edge of the opposing party's heat transfer plate, measure above-mentioned distance similarly to Example 1, result is also 19 places at 90% of measuring point is 17.5 ± 0.2mm.The difference that plate-type reactor D is equivalent to measured value and above-mentioned design load is the situation of+2.5mm.In the reaction, the peak temperature of catalyst layer, more than 450 DEG C, has the possibility causing runaway reaction, thus stops reaction for the time being.Be reduced to except 300 DEG C except by the temperature of thermal medium, implement reaction similarly to Example 1, but conversion ratio be no more than 50%, reaction is not carried out.
(embodiment 4)
The plate-type reactor E with two reaction zones territory is used to carry out the oxidation of propylene.In plate-type reactor E, the first conversion zone is the structure identical with plate-type reactor B.The structure that the plate-type reactor that second reaction zone after the first conversion zone is is 16mm with the minor axis of heat-transfer pipe (H), the length of conversion zone is 400mm, the axle base of heat transfer plate is 27.5mm is identical.
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 flange of side's heat transfer plate and the recessed edge of 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 the second reaction zone of plate-type reactor E, the design load of the distance between the surface of heat transfer plate is the distance between the flange of side's heat transfer plate and the recessed edge of the opposing party's heat transfer plate, is 18.5mm.In addition, measure similarly to Example 1 to above-mentioned distance, result is also 13 places at 87% of measuring point, and measured value is 18.5 ± 0.2mm.The difference that second reaction zone is equivalent to measured value and mean value in the distance between the surface of heat transfer plate is the situation of+1.5mm.
In each conversion zone, in order to make the peak temperature of catalyst layer identical with the peak temperature of the catalyst layer in embodiment 1, make that the temperature of thermal medium in the first conversion zone is 330 DEG C, the temperature of thermal medium is 328 DEG C in second reaction zone, in addition, the condition identical with embodiment 1 is adopted to implement to react.Its result is as shown in table 2, obtains reaction achievement excellent similarly to Example 1.
(comparative example 2)
The plate-type reactor F with two reaction zones territory is used to carry out the oxidation of propylene.In plate-type reactor F, the first conversion zone is the structure identical with plate-type reactor D, and second reaction zone is identical with the second reaction zone in embodiment 4.The difference that the first conversion zone in plate-type reactor F is equivalent to measured value and above-mentioned design load is the situation of+2.5mm, and the difference that the second reaction zone in plate-type reactor F is equivalent to measured value and above-mentioned design load is similarly to Example 4 the situation of+1.5mm.
Except make the temperature of thermal medium identical with embodiment 4 except, implement to react with the condition identical with embodiment 1, its result, the peak temperature of catalyst layer, more than 450 DEG C, has the possibility causing runaway reaction, thus stop for the time being reaction.Be reduced to except 300 DEG C except by the temperature of the thermal medium in the first conversion zone, implement reaction similarly to Example 1, but conversion ratio be no more than 50%, reaction is not carried out.
(embodiment 5)
As plate-type reactor, in order to filling test use, make the device shown in Figure 16.6 heat transfer plates are set.The length (width of heat transfer plate) of the heat-transfer pipe axis in 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 heat transfer plate height of the heat transfer plate axis begun from this vent board is 1.88m, and the line part without heat-transfer pipe forms 150mm upward from above-mentioned vent board.Dividing plate is arranged with 50cm interval.Dividing plate is the device of shape shown in Figure 17, and its thickness of slab is 5mm.
Heat transfer plate makes in the following way: the consecutive shape of bead that stainless steel (SUS304L) steel formability processed being 1mm by thickness of slab is formed between recess and recess for its cross sectional shape is arc-shaped, and the above-mentioned bead in two steel plates after shaping be welded to one another, thus produce heat transfer plate.In this heat transfer plate, the specification of heat-transfer pipe as described in Table 3.In addition, in above-mentioned plate-type reactor, the above-mentioned line part spacing in adjacent heat transfer is 24mm.
[table 3]
Major diameter (mm) Minor axis (mm) Heat-transfer pipe number
1st conversion zone 2a 50 20 12
2nd conversion zone 2b 40 16 11
3rd conversion zone 2c 30 10 23
In above-mentioned plate-type reactor, catalyst filling in the section formed by adjacent heat transfer and dividing plate.Catalyst uses the catalyst obtained as follows: 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), it is shaping, be shaped to external diameter 4mm Φ, highly 3mm's is cylindric, fire, obtain catalyst.Herein, Mo, Bi, Co, Ni, Fe, Na, B, K, Si, O are atomic symbol, and (x) of O (x) is the value determined by the state of oxidation of each metal oxide.
In the filling of catalyst, the interval 50cm of use and dividing plate has the vibrating feeder (conveyer) of same widths.With the filling speed of 1L (liter)/following (about 0.8 ~ 0.9L/min) per minute, catalyst is supplied to above-mentioned zone.In more detail, measure the catalyst of 11.6 liters, prepare 33 bags of catalyst be sub-divided into respectively in 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 packed layer height, making the even of formed catalyst layer above, measuring the distance with the upper end of heat transfer plate, by the difference determination packed height of this distance with the height of the heat transfer plate begun from above-mentioned vent board.Being determined in a section of this distance carries out 11 places with the interval of 5cm.Depend on that the catalyst feed rate of vibrating feeder (conveyer) has fluctuation, also have the situation that feed speed temporarily becomes large.During feed speed extreme deviations, catalyst layer height becomes large, sometimes bridge joint occurs, and also has the situation that region is overflowed between heat transfer plate; Now, take the latch for printed circuit being installed on bottom, region, unload vent board, extract catalyst out, again fill.For recharging, if add up to enforcement 3 times ading up in the filling operation of 300 times, be sufficient.
According to filling the measurement result of floor height, the floor height of catalyst layer differs with theoretical value ± 5cm within.The height of catalyst layer has the ± deviation of 2.7% relative to above-mentioned theory value.From this result, have in the plate-type reactor of dividing plate above-mentioned, by catalyst filling in each section above-mentioned, can very equably to above-mentioned gap-fill catalyst.
(embodiment 6)
As described below in the computational methods relating to the conversion ratio of reaction raw materials used in the present embodiment of the 3rd manufacture method of reaction product, the selection rate of goal response product, the yield of goal response product and the load of reaction raw materials.
The conversion ratio [%] of <1> reaction raw materials (propylene, methacrylaldehyde etc.)=
(being converted into the molal quantity of the reaction raw materials of other material in reactor)/(being supplied to the molal quantity of the reaction raw materials of reactor) × 100
Selection rate [%]=(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 reactor) × 100 of <2> goal response product
The yield [%] of <3> 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
The load [NL/Lhr] of <4> reaction raw materials=
The catalytic amount L [liter] of the quantity delivered L per hour [liter] of reaction raw materials [converting through standard state]/be supplied to reaction
Herein, so-called standard state refers to the state being in temperature 0 DEG C, pressure 101.325kPa (absolute pressure).
When utilizing molecularity oxygen to carry out catalytic gas phase oxidation to manufacture acrylic acid to propylene, as being 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), carry out shaping to it, obtain the cylindric beaded catalyst of external diameter 4mm Φ, 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), by this powder compacting, obtain the ring catalyst of external diameter 5mm Φ, internal diameter 2mm Φ and height 3mm.Herein, (x) of O (x) is the value determined by the state of oxidation of each metal oxide.
The reactor of structure shown in Figure 42 is used in plate-type reactor.By thin corrosion resistant plate (thickness of slab 1mm) 2 chip bondings of waveform shape, the thermal medium body stream that forming reactions temperature regulates.The cycle (L) of the waveform shape shown in Figure 43, highly (H) and wave number list in table 4.
In leading portion reactor, fill leading portion catalyst, in backend reactors, fill back segment catalyst, thus form catalyst layer in a pair waveform heat transfer plate after this joint.For the catalyst layer in leading portion reactor and backend reactors, all rise according to the upstream of the flow direction of the specification of waveform shape autoreaction gas as shown in table 4 and be divided into conversion zone (S1), conversion zone (S2) and conversion zone (S3).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 to 26mm.The width of heat transfer plate is 114mm.
[table 4]
Catalytic amount shown in table 4 is following volume determination, and this stereometry makes each reactor vertical, at catalyst layer foot installing plate, and is injected by top that water carries out measuring.This catalytic amount is used for the calculating of the load of reaction raw materials.
As reaction raw materials, pass into the reacting material mixture (hereinafter referred to as reaction mixture gas body) containing 9.5 % by mole of propylene by the entrance (conversion zone (S1)) of leading portion reactor.In reaction mixture gas body, in addition to propylene, also containing 15.2 % by mole of oxygen, 65.9 % by mole of nitrogen and 9.4 % by mole of steam.
In the leading portion reactor shown in table 4, fill above-mentioned leading portion catalyst, carry out the oxidation reaction of propylene.Thermal medium body uses the NeoSK-OIL (registration mark) 1400 combining and grind Tecnix (strain) society and manufacture, and after carrying out temperature adjustment respectively, is supplied to conversion zone (S1) ~ conversion zone (S3).The quantity delivered of thermal medium body makes the flow velocity of thermal medium body be more than 0.7m per second.
By density of propylene be the reaction mixture gas body of 9.5 % by mole with 5, the ratio of 670 liter per hour [converting through standard state (temperature 0 DEG C, 101.325kPa)] is supplied to the entrance of reactor.In addition, be supplied to each conversion zone (S1), the temperature of thermal medium body of (S2) and (S3) is respectively 342 DEG C, 329 DEG C and 329 DEG C.The quantity delivered of propylene is 539 liter per hour [converting through standard state (temperature 0 DEG C, 101.325kPa)] (hereafter also referred to as NL/Hr).The pressure of reactor inlet is 0.109MPaG (MPa gauge pressure), the entrance of the catalyst layer of reactor and the pressure differential (pressure loss) of outlet very little, be 14kPa.
Utilize gas chromatography to analyze exit gas, the conversion ratio of result propylene is 97.2%, acrylic acid yield is 10.1%, the yield of methacrylaldehyde is 81.7%.The load of propylene is 167 liter per hour [converting through standard state (temperature 0 DEG C, 101.325kPa)] (hereafter also referred to as NL/LHr).
(embodiment 7)
Except by being supplied to each conversion zone (S1), the temperature of thermal medium body of (S2) and (S3) is adjusted to except 360 DEG C, 345 DEG C and 329 DEG C respectively, implements reaction similarly to Example 6.Utilize gas chromatography to analyze exit gas, the conversion ratio of result propylene 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 hour [converting through standard state (temperature 0 DEG C, 101.325kPa)] and by being supplied to each conversion zone (S1), the temperature of thermal medium body of (S2) and (S3) is adjusted to 342 DEG C, 335 DEG C and 334 DEG C respectively, implements reaction in addition similarly to Example 6.The feed speed of propylene is 743NL/Hr.
Utilize gas chromatography to analyze exit gas, the conversion ratio of result propylene is 95.4%, 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 is 0.134MPaG (MPa gauge pressure), the pressure loss of the catalyst layer of reactor is 30kPa (kPa).
(embodiment 9)
The reactor outlet gas that embodiment 8 obtains is supplied to backend reactors, methacrylaldehyde is oxidized, manufacture acrylic acid.As the supply source of the molecularity oxygen for oxidation reaction, by air with 2,186 liter per hour [converting through standard state (temperature 0 DEG C, 101.325kPa)] and nitrogen mix with leading portion reactor outlet gas with 680 liter per hour [converting through standard state (temperature 0 DEG C, 101.325kPa)], are supplied to backend reactors.
Be supplied to each conversion zone (S1) of backend reactors, the temperature of the thermal medium body of (S2) and (S3) is respectively 284 DEG C, 278 DEG C and 278 DEG C.The quantity delivered of thermal medium body makes the flow velocity in the thermal medium body stream of each conversion zone be more than 0.4m per second.The pressure of backend reactors entrance is 0.097MpaG (MPa gauge pressure), and the pressure loss of the catalyst layer of reactor is 29kPa (kPa).
Utilize gas chromatography to analyze exit gas, the conversion ratio of result methacrylaldehyde is 99.4%, acrylic acid is 86.3% relative to the yield of the propylene being supplied to leading portion reactor.The load of methacrylaldehyde is 201NL/LHr.
(embodiment 10 ~ 12 and comparative example 3 and 4)
The reaction mixture gas body making reaction used is the composition of propylene 9.4 % by mole, oxygen 15.2 % by mole, 65.9 % by mole, nitrogen and steam 9.5 % by mole, propylene is supplied with load 219NL/LHr, and by being supplied to each conversion zone (S1), the temperature of thermal medium body of (S2) and (S3) is adjusted to the temperature shown in table 2, in addition, reaction is implemented similarly to Example 6.The analysis result utilizing gas chromatography to carry out the exit gas analyzed lists in table 5.Next carry out the reaction of more than 230 hours, conversion ratio and stable yield, there is no the sign demonstrating catalyst degradation.
[table 5]
(embodiment 13 and comparative example 5)
The plate-type reactor used is above-mentioned leading portion reactor, identical with ripple plate interval P with cycle (L), highly (H) shown in table 4, wave number, but the width of heat transfer plate is 96mm.Above-mentioned back segment catalyst is filled in this heat transfer plate-type reactor.Packed height is 1.8m, catalytic amount is 2.5L (liter).
As comparative example 5, prepare following tube-type reactor, that is, use the stainless steel tubulation of internal diameter 27mm as reaction tube, in this reaction tube, fill back segment catalyst until packed height is 1.8m.Catalytic amount is 1.0L.
Fix vertical with tube-type reactor for above-mentioned plate-type reactor, supplied the air of room temperature by top, measure inlet pressure and outlet pressure, obtain the pressure loss of catalyst layer.The results are shown in table 6.
[table 6]
Throughput [NL/LHr] represents catalyst 1L (liter), the gas delivery volume of every 1 hour herein.In addition, the volume of gas uses the volume converted through standard state (0 DEG C, 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 change and correction not departing from the spirit and scope of the present invention.
The Japanese patent application (Japanese Patent Application 2008-091818) that the Japanese patent application (Japanese Patent Application 2008-091705) submitted in the Japanese patent application (Japanese Patent Application 2008-091298) that the application submitted to based on March 31st, 2008, on March 31st, 2008, on March 31st, 2008 submit to and the Japanese patent application (Japanese Patent Application 2008-327973) that on December 24th, 2008 submits to, introduce this description with the form of reference by above-mentioned application content.
Industrial applicibility
Plate-type reactor its make in, due to the configured offset design load of heat transfer plate, therefore can not get in the plate-type reactor of reality design time anticipation desired by reaction achievement.But, in first plate-type reactor and preparation method thereof, provide the configuration of special provision heat transfer plate admissible error and in the technology of this error range internal fixtion heat transfer plate.Thus, by when not being attended by the change of plate-type reactor structure to the first manufacture method of the reaction product that heat medium temperature controls, establish the technology for realizing the reaction achievement desired by actual plate-type reactor, and can expect significantly to expand 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, expect the further development in the manufacture field based on the catalytic reaction product of gas phase.
In addition, in plate-type reactor, the thickness sometimes carried out by adjusting catalyst layer controls reaction.In such plate-type reactor, in reactor monolith, uniform filling catalyst is more difficult, but the second plate-type reactor rapidly, accurately and easily can carry out the suitable filling of catalyst, and can expect the setting of plate-type reactor, the significantly improving of maintenance care and the workability in making regular check on.
In addition, according to the second manufacture method of reaction product, to supply response raw material in the plate-type reactor being filled with catalyst, this reaction raw materials is reacted manufacture in the manufacture method of product, the reduction of the reaction achievement preventing the fluctuation of packed catalyst state from causing can be expected, the further raising of reaction achievement realizing the anticipation reaction achievement corresponding to catalyst performance and bring through the catalyst of improvement.
In addition, according to the 3rd manufacture method of reaction product, to supply response raw material in the plate-type reactor being filled with catalyst, this reaction raw materials is reacted manufacture in the manufacture method of product, when improving the processing load amount of reaction raw materials of unit catalyst, the increase of the pressure loss of the reacting gas by catalyst can be prevented, and by suitably controlling to react the heat that produces to prevent heat spot, the yield of goal response product can be improved while preventing catalyst from damaging.
Therefore, industrial value of the present invention is remarkable.

Claims (7)

1. the preparation method of a plate-type reactor, this plate-type reactor having reaction vessel for making gaseous feed react, being disposed side by side on more than 2 heat transfer plates in described reaction vessel and the thermal medium feedway for the thermal medium to the desired temperature of described heat transfer plate supply
Described heat transfer plate comprises more than 2 heat-transfer pipes linked with the periphery of cross sectional shape or ora terminalis,
Described thermal medium feedway is the device of the heat-transfer pipe supply thermal medium to the heat transfer plate be contained in reaction vessel;
The feature of this preparation method is,
It comprises following operation: with the design load of the distance between the surface of described heat transfer plate be 5 ~ 50mm, the measured value of distance between described surface and the difference of described design load be that the interval of-0.6 ~+2.0mm configures heat transfer plate, heat-transfer pipe is engaged with thermal medium feedway, distance between the surface of described heat transfer plate is in the gap between relative heat transfer plate, distance on the direction orthogonal with apart from equidistant, the face be made up of the axle of described heat transfer plate
Described preparation method comprises following operation further: across forming the sept at described interval between heat transfer plate, before engaging with thermal medium feedway, configure heat transfer plate in reaction vessel.
2. the preparation method of plate-type reactor as claimed in claim 1, it is characterized in that, the length of the axis of described heat transfer plate is below 5m.
3. the preparation method of plate-type reactor as claimed in claim 1, it is characterized in that, the upstream side in the ventilation direction of the measured value of the distance between described surface and the unstrpped gas of difference in described gap of described design load is less.
4. the preparation method of plate-type reactor as claimed in claim 1, it is characterized in that, the raw material reaction rate in described unstrpped gas is that the measured value of distance between the position of less than 70%, described surface and the difference of described design load are less than and are greater than the measured value of the distance between the position of 70%, described surface and the difference of described design load in described reactivity.
5. the preparation method of plate-type reactor as claimed in claim 1, it is characterized in that, the total measurement (volume) in described gap is more than 3L.
6. the preparation method of plate-type reactor as claimed in claim 1, it is characterized in that, described plate-type reactor has temperature measuring apparatus further, this temperature measuring apparatus for measure the catalyst layer formed in described gap by packed catalyst 2 places more than the temperature of position.
7. the manufacture method of a reaction product, this manufacture method is used in reaction vessel and is provided with more than 2 heat transfer plates side by side, gap-fill between heat transfer plate has catalyst and forms the plate-type reactor of catalyst layer, and described manufacture method comprises and gaseous feed is supplied to described reaction vessel and by the operation of described catalyst layer and to the operation of thermal medium of more than 2 heat-transfer pipes supply predetermined temperatures forming described heat transfer plate, described manufacture method makes unstrpped gas react and generate the reaction product of gaseous state under the existence of described catalyst;
The feature of described manufacture method is, the plate-type reactor by the preparation method gained described in any one of claim 1 ~ 6 is used as described plate-type reactor;
Thermal medium is supplied to heat-transfer pipe, and the temperature of this thermal medium is the temperature of the setting value of the peak temperature of the catalyst layer that to make the peak temperature of described catalyst layer be plate-type reactor set when designing.
CN201510118088.1A 2008-03-31 2009-03-30 Manufacturing method for plate type reactor Pending CN104707540A (en)

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JP2008-091818 2008-03-31
JP2008-327973 2008-12-24
JP2008327973A JP6088120B2 (en) 2008-12-24 2008-12-24 Plate type reactor, method for producing the same, and method for producing a reaction product using the reactor

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