CN106955645A - Reactor for performing heat release or the endothermic reaction - Google Patents

Reactor for performing heat release or the endothermic reaction Download PDF

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Publication number
CN106955645A
CN106955645A CN201611175285.8A CN201611175285A CN106955645A CN 106955645 A CN106955645 A CN 106955645A CN 201611175285 A CN201611175285 A CN 201611175285A CN 106955645 A CN106955645 A CN 106955645A
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reactor
reaction
hot plate
catalyst
heat
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Inventor
弗兰克·卡斯提罗-维尔他
马丁·罗泰梅尔
斯特凡·哈格
林林
克里斯托弗·德罗斯德措
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Publication of CN106955645A publication Critical patent/CN106955645A/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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • 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
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0278—Feeding reactive fluids
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0285—Heating or cooling the reactor
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0292—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds with stationary packing material in the bed, e.g. bricks, wire rings, baffles
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
    • B01J8/0453—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being superimposed one above the other
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0492—Feeding reactive fluids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
    • B01J2208/0015—Plates; Cylinders
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00893—Feeding means for the reactants
    • B01J2208/0092—Perforated 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
    • B01J2208/021—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles comprising a plurality of beds with flow of reactants in parallel
    • B01J2208/022—Plate-type reactors filled with granular 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
    • B01J2219/18—Details relating to the spatial orientation of the reactor
    • B01J2219/182—Details relating to the spatial orientation of the reactor horizontal
    • 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
    • B01J2219/2461—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
    • B01J2219/2476—Construction materials
    • B01J2219/2477—Construction materials of the catalysts
    • B01J2219/2481—Catalysts in granular from between plates

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to the reactor for performing heat release or the endothermic reaction, particularly it is used for at least two reaction compartment reformed gas and/or the reactor and technique of liquid reaction medium for being at least partially filled with catalyst, reactor is formed as being disposed with least three Heat transmission spaces of arrangement substantially parallel to one another in the reactor, and Heat transmission space thus at least in part separates each reaction compartment each other.Each is formed by least one hot plate in Heat transmission space, and each of which hot plate is made up of the two boards being connected to each other at multiple other positions of edge and surface.In operation, horizontal-extending vertical extension more than it of the reactor at least one axis.The entrance and exit for reaction medium is also provided with, so that reactor is vertically crossed by reaction medium.

Description

Reactor for performing heat release or the endothermic reaction
Technical field
The present invention relates to at least two reaction compartment reformed gas or liquid with catalyst filling at least in part The reactor of precursor reactant medium, the reactor is formed as setting at least three heat of arrangement substantially parallel to one another to pass in the reactor Defeated space, these Heat transmission spaces at least in part separate each reaction compartment each other, and wherein each is equal in Heat transmission space Formed by least one hot plate, and each of which hot plate is made up of two boards, edge quilt of the two boards at them Weld together, and the multiple spot welding for equally connecting these plates are assigned on the surface of the two boards.The present invention is also related to And the technique for the reaction controlling in this reactor.
Background technology
Many typical heterocatalysis gas phase reactions are performed in so-called fixed bed reactors.In the process, it is catalyzed The bed (fixed bed) of agent particle or be coated with catalyst carrier each crossed by reaction medium.Afterwards, reacting fluid Heat exchanger is flowed through, so as to the obtained reaction that dissipated at least in part before reacting fluid enters in next catalyst bed Heat.Alternatively, also temperature reduction can be realized for the material stream quenched by introducing.Generally, typical reactor has 4 to 6 fixed beds laterally.
By the structure for using the example for converting methanol into propylene (MTP techniques) that these fixed bed reactors are explained in greater detail Make.Fig. 1 shows to be generally used for the reactor for converting methanol into propylene.Via conduit 13 and 131Methanol is supplied to overhead Reactor 10.From reactor 10, methanol arrives at fixed bed 11 on gravity direction first1Place, in the fixed bed 111Place, at least Part methanol is converted into propylene.Carried out with exothermic heat of reaction, reaction heat is released, reaction heat is in heat exchanger 121Middle consumption Dissipate.Alternatively, also temperature reduction can be realized for the material stream quenched by introducing.However, being used as quenching by addition The correspondence regulation material stream (for example, methanol) of stream, can also enter subsequent fixed bed 112Preferred temperature is realized before.
Afterwards, the mixture of oxide (being preferably methanol), propylene and other reaction products enters fixed bed 112In.Through By conduit 132, fresh oxide here is generally fed to the top of actual fixed bed again, thus, it is possible to additionally control Make the conversion in each fixed bed and thus also control obtained heat.Afterwards, in heat exchanger 122Upper guiding isolation Product mixtures.In fixed bed 113、114、115With 116And corresponding heat exchanger 123、124、125With 126And feeding is led Pipe 133、134、135With 136The middle repetition process.Finally, product mixtures are extracted via conduit 14.
In typical MTP factories, each is respectively provided with three these reactors, all parallel work-flows of each two reactor, And the 3rd standby, or to catalyst regeneration.Sent out in DE 10 027 159 or also in US 2009/0124841 Existing this factory and the modular design of technique.After catalyst regeneration is completed, reactor is operated again by the catalyst of regeneration, And the reactor of the catalyst comprising most long service life is supplied to regeneration now.Thus, in typical production line, all the time 2 Individual reactor is in the operator scheme for performing reaction, but this 2 reactors are filled with urging with different ageing states Agent.
Present reaction design needs about 2000m3The larger reaction of (for the plant capacity of about 450kta propylene) Device volume, this is as caused by following facts：In addition to adiabatic catalyst beds, it is also necessary to heat exchanger or quenching section Form provides the cooling zone having been mentioned.Moreover, must be provided with correspondence space is used to filling and discharging catalyst.
Generally, six fixed beds are disposed in over each other, these fixed beds each be respectively provided with 20 to 60cm height. In each reactor, about 150Mt catalyst is dispensed in this six catalyst beds, and the total amount of catalyst increases with implantation Greatly.This means will be seen that less catalyst in the first catalyst bed, thus react can not deliberately carry out completely herein, and It is to be limited by catalytic amount.This should prevent that too many part produces the out of control of the caused reaction of heat due to exothermic reaction.By most The fact that the 6th fixed bed afterwards includes the maximum amount of catalyst, it can be ensured that methanol is by complete or approximately fully convert.
Generally, exist in each fixed bed by approximate 100 compartments of catalyst filling respectively.With the present invention's Design (only one bed) is compared, and this technique is relatively expensive.When fixed bed is crossed by catalyst, it should carefully cause that catalyst exists It is all uniform close on all compartments, to avoid local catalyst from damaging.In addition, it is also necessary to avoid catalyst from being contacted with liquid, Because this can result in the permanent damage of catalyst.In order to adjust the temperature in each fixed bed, by Partial Conversion Reaction medium also mixed with fresh reactant medium.
In addition, must carefully cause occur the alap pressure loss via fixed bed in the reactor, to ensure To the selectivity of target product (short-chain olefin, particularly propylene).
As explained above, being currently used for being typically more than the reactor design of 450,000t/ usual propylene yield needs Larger reactor volume and corresponding reactor diameter, to minimize the pressure loss.It is thus impossible to which easily reactor is set Count still larger, and construction and transport are also limited.
In a word, in the plant construction (especially with regard to the challenge of very big reactor volume and diameter, reaction medium Property distribution and relatively expensive catalyst treatment) in non-be commonly present improved potentiality.
The content of the invention
It is therefore an object of the present invention to provide a kind of reactor with reduced size, it is able to carry out in the reactor Exothermic reaction particularly MTP reacts, wherein the distribution of the uniform temperature with low pressure loss is the target of the design.Except processing Outside, it should especially promote to be filled with raw catelyst.
The purpose is solved by a kind of reactor.
This reactor for reformed gas or liquid reaction medium includes being at least partially filled with catalyst extremely Few two reaction compartments.These reaction compartments are formed to be disposed with least three of arrangement substantially parallel to one another in the reactor Heat transmission space.In the sense of the present invention, the route in Heat transmission space +/- 20 ° of maximum deviation each other are substantially meant, it is excellent 10 ° are selected, particularly preferred 5 °, 2 ° are particularly preferred very much.Each is reacted at least in part in these each parallel Heat transmission spaces Space is separated each other.
Heat transmission space each formed by least one hot plate.In the sense of the present invention, hot plate is by two boards structure Into the two boards are preferably welded together in their edge connection, and are assigned on the surface of the two boards Same multiple additional tie members (being preferably spot welding) that two boards are connected to each other.These plates can by robot or machine with Automatic mode and thus produced with low-down price.After welding, these plates by shaped by fluid pressure (typically by high pressure Under liquid in pressurize) and expand, thus acquisition cushion passage between the plates.
Via Heat transmission space, heat energy can be provided to reaction and be removed from reaction, wherein hereinafter mainly will Exothermic reaction is discussed, in exothermic reaction, correspondingly needs to remove heat energy.
Subject of the present invention is now：In operation, reactor is horizontal-extending more than reaction at least one axis The vertical extension of device.This means the flux of reaction medium is perpendicular to the horizontal axis extension of reactor.Hot plate can be directed To be parallel to each other on a horizontal axis in reactor or perpendicular to horizontal axis.
Compared with previous reactor, the arrangement in the reactor of the present invention is changed.It is provided for reaction medium Entrance and exit, so that reactor is vertically crossed by reaction medium.Preferably implement it is through-flow, so as to flow direction and gravity Direction is in line.This has the advantages that to be unable to recurring structure change in the fixed bed of catalyst in through-flow period.
The Creative Design for being formed as the small reactor of height over width provides multiple advantages.On the one hand, in principle can The various fixed beds of the heat exchanger with intervention are omitted, but hot plate is set in indivedual fixed beds.
On the other hand, the size with the significant lower pressure loss is obtained now, because the stream of reaction medium is necessary Separated in the top of each reaction compartment, to be passed through each reaction compartment.Then, in each case, reaction medium is all only Flow through a stationary catalyst bed of the vertical height with reactor, rather than flow through as previous usual embodiment multiple solid Fixed bed.In meaning of the present invention, term reactor container means the container of the inside of reactor, and the container at least includes Hot plate and their gap, and the container (preferably entirely) is filled with catalyst at least in part in the term.Instead Answering the path length being substantially reduced of medium also causes the significant lower pressure loss.Due to the path length of the reduction of reaction medium Degree, the condition generally along the path length covered by reaction medium is traversed than reactor along significantly longer vertical path Reactor design it is equably many.This causes the following fact：In the reactor according to the present invention, reaction controlling can substantially more Carried out close to ideal isothermal reaction condition, it is thus possible to form less accessory substance and more desired product such as propylene.
In addition, it will be apparent that simplify the replacing of catalyst, because preferably one bed of less bed must be changed here, rather than it is used 6 fixed beds of the common practice such as in MTP techniques.In addition, reactor has significantly smaller diameter, fortune is thus greatly simplified Defeated and construction.
Finally, to have the advantage that it is allowed for larger and very simple compared with small capacity for this reaction utensil Design, is such as 10 hot plates at least forming 10 Heat transmission spaces from critical quantity, it has to be assumed that in each reaction compartment Reaction condition it is all identical, it is thus possible to the number of reaction compartment is directly calculated by the simple multiplication of the amount based on desired product Mesh.Meanwhile, also final make the small amount of reactor of conversion it is possible that growing to so that the reactor required than it is specific most The previous reactor of small size is also more convenient compared to particularly for semiworks.Produced especially for from renewable raw material Methanol approach (will necessarily cause methanol further processing it is decentralized), it is this design it is very promising.In principle, can The yield less than 100kt propylene/year is realized by this design.
Moreover, by only one fixed bed, so-called decatize (i.e. with steam pre-treatment catalyst) is greatly simplified, because To still have to handle only one fixed bed, thus preferably Temperature Distribution of the control during steaming operation is possible.
Reactor size is preferably designed such that：People works wherein without any problem, and all zero Part is easily accessible.This especially simplifies maintenance work.But, it is especially useful in the smaller reactor size of your pupil's production yield is also can Capable.
In addition, being preferred when reaction compartment vertically extends along the extension in Heat transmission space.In practice, this is meaned ：Stationary catalyst bed is exclusively found in the bottom (operating the region nearest from the earth's surface) of reactor and without heat Plate, is adiabatically carried out herein so as to react.Because the region that this, which is reaction medium, has largely been converted is (because reaction is situated between Matter vertically flows through stationary catalyst bed along longest path length), so due to adiabatic reaction condition energy at this point Enough completions for realizing conversion.
It has also been found that when hot plate additional tie members preferred point welding position when on straight line it is favourable, its cathetus is by the fact that limit It is fixed：Corresponding adjacent welds are located on straight line.Each the mutual distance of point being preferably located on straight line is same distance all the time D3, and straight line has same distance d5 all the time each other, that is, extends parallel to.It is offset from one another when the point on each straight line is arranged to It is particularly preferred when being only found so as to straight line in a dimension.This generation similarly ensure be used for optimal heat exchange and Thus the system of enough passages of the uniform temperature on whole hot plate.
In a particularly preferred embodiment, it is preferably that the cushion having been mentioned between spot welding leads to that hot plate, which is included in additional tie members, Road, in these passages, the mutual ultimate range of two boards is apart from d2.Meanwhile, the distance between two adjacent hot plates It is referred to as d1.Between two adjacent hot surfaces and therefore according to the present invention, the reaction compartment is consistently greater than d2 apart from d1 (i.e. hot plate is preferably the largest extension between spot welding in two additional tie members).Meanwhile, it is consistently less than apart from d1 apart from d2 100 times.Therefore, one aspect of the present invention is：Particularly when the two geometric parameters are by accordingly adaptation, It is able to ensure that the favourable isothermal reaction control having been mentioned.
When the distance and thus the width d1 of reaction compartment be between 1.5 times and 10 times of d2 of d2 when be especially excellent Choosing.Very especially for from methanol production propylene, this causes peak optimization reaction control, wherein stationary catalyst bed can be excluded In focus as it is too cold so that do not react or even occur methanol condensation point.
One aspect of the present invention is a kind of integrated equipment for removing catalyst.This equipment can for example be designed Make it possible to be opened the support surface of catalyst by fold mechanism, so that catalyst is fallen.Another special section space-efficient design Regulation：The support surface of catalyst is divided at least two parts, and supports catalyst in orbit, it is every so as to support surface A part can be pulled to the lower section of corresponding another part, thus catalyst is fallen by gravity.
It is designed such that they are adapted to guiding fused salt in addition, the specificity of the present invention is hot plate.Except on temperature point Outside the optimization guiding of cloth, the passage in hot plate is also constructed such that：In the case where shutting down or being retired, it is ensured that by means of weight Power is almost emptied completely the cavity in hot plate.Thus do not leave the salt of solidification in hot plate after the cooling of equipment, and reduce heat The impaired risk of plate.Therefore also accordingly promote to be on active service again.Had the following advantages that using fused salt：Made with usual using high steam Compared for heat transport medium, the wall thickness of hot plate can be significantly smaller, because pressure load is accordingly relatively low.Heat transfer is thus again Forcefully improved.Low-pressure is in such as in the use of fused salt in hot plate, will be preferably selected in 0.5 and 1.5mm/ plates Between wall thickness (hot plate is made up of 2 blocks of plates) --- for build the reason for, some manufacturers are preferably not less than 1mm.With In the system of high pressure, the wall thickness between 1.5 and 3mm will be rather may be used at --- it is hardly feasible more than 3mm, because plate It is no longer able to accordingly deform, but is designed here by 3mm, has been able to realize the pressure apparently higher than 100bar.
In addition, also can be by the use of high steam as heat transport medium, when using hot plate often.This high steam With up to 100bar pressure, therefore with corresponding thermal capacity.Larger factory integration body is generally configured with having difference The vapour system of pressure (high, neutralization low-pressure steam), these vapour systems are adapted to the conduct energy between each plant component, and And which part obtain electric power from produced steam.Therefore, particularly in factory integration body, by according to the anti-of the present invention It is recommendable to answer device type to be introduced into this high pressure steam system.
Another aspect of the present invention is provided：Reaction compartment and associated Heat transmission space filled with catalyst bed are determined Size, so as to the catalyst for every cubic metre, reactor includes at least one hot plate, and/or every cubic metre of catalyst bed With at least 10m2Cooling surface, wherein cooling surface directly constitutes the surface of one block of plate in the two boards of hot plate.This leads Cause the surprising simplified correlation of the total amount on used hot plate.
Another aspect of the present invention is provided：In each hot plate, such as by the hole in hot plate, from a reaction compartment to Another reaction compartment sets passage opening, wherein the two boards are tightly attached to each other by the circular weld at this some holes. By these additional openings, reaction medium can be mixed via reaction compartment, thus, it is possible to therefore further increase the equal of product One property.
In addition, the present invention includes a kind of equipment, wherein reactor provides gas distributing device, and the gas distributing device will be anti- Distribute with answering homogeneous media on all reaction compartments.The gas distributing device of this distributor also can be distributor chamber, multiple (the multiple opening for example can also be designed to slit to opening, and these slits are for example along or transverse to horizontal reactor Axis extend) or nozzle make reaction medium from the distributor chamber flow into reactor reaction compartment in, thus, it is possible to realize in institute There is the highly uniform distribution on reaction compartment.Equally also it is possible that：Not by distributor chamber, via in the top of reaction compartment Nozzle be introduced directly into reaction medium, from these nozzles by reaction medium distribute in each reaction compartment.In principle, it is feasible It is：Operated with larger or smaller nozzle amount and corresponding connection valve and pipe, or but by each nozzle and associated Equipment Design it is larger.Big number of nozzle has the following advantages that：, can be as uniform as possible in an optimal manner in the sense that distribution The distribution of reaction medium is realized on ground, and on the difference in differential responses space close to flow rate, higher flexibility is also can Can.
Also catalyst member can be placed in reaction compartment by corresponding grid or another device.This has The advantage that carrier structure can be incorporated to, carrier structure can also be removed from reaction compartment again together with catalyst.
Also advantageously：Apply net and/or inert material in the top of catalyst, so as to which catalyst to be placed on and react In that region faced that becomes a mandarin of medium, particularly heat transport medium or this still heat that just start that becomes a mandarin are not being provided also At the point of dissipation reduction.Therefore, it is possible to additionally guard catalyst.
In addition, also it is possible that：Also inert material is concomitantly introduced into catalyst bed, it is close to reduce the catalyst in bed Degree, thus also reduce local reaction rate.It can also be envisaged that non-homogeneous catalyst bed, by the non-homogeneous catalyst bed, can be added Ground influences local reaction rate.
Subject of the present invention also resides in a kind of reformed gas in the reactor or the technique of liquid reaction medium.This reaction Device includes at least two reaction compartments crossed by reaction medium for being at least partially filled with catalyst.Reaction compartment is by each other At least three Heat transmission spaces being arranged substantially in parallel are formed, and wherein heat transport medium flows through Heat transmission space.
Each Heat transmission space is made up of at least one hot plate, and each of which hot plate is then made up of two boards, institute State two boards to be welded together in their edge, and distributed on the surface of the two boards and equally connect these plates Multiple spot welding.
Subject of the present invention is：Reaction medium vertically flows through reactor (preferably on gravity direction), and reacts The horizontal-extending vertical extension more than reactor at least one axis of device.This provides and significantly simplify catalyst Loading and the advantage of unloading.
Further, since overall relatively narrow diameter, reactor is also easily processed much in itself.It can also be envisaged that with relative to current The reactor of the yield for the 100-250kt/ or also smaller that plant output size reduces converts methanol into the example of propylene.
It is thus conclusive to be：Very uniform stream realizes isothermal reaction control close to catalyst bed, while pressure Loss is lower than in the case of traditional reaction controlling.
One aspect of the present invention is：Heat transport medium is guided to reaction medium with cocurrent.This has the following advantages that：Instead The maximum temperature difference between medium and heat transport medium is answered to occur in the region that reaction medium enters reaction compartment, in the region, In the case of exothermic reactions, partly exist highest conversion degree and thus there is also heat most development.
However, also it is possible that with adverse current or even with cross-current (depend on can relative to reaction medium flowing The arrangement for the hot plate that direction is vertically movable and horizontally oriented) supply heat transport medium, because usually can produce by this way More uniform Temperature Distribution.
Furthermore it is possible to use any type of heat transport medium in liquid or gas form.Because liquid heat conveyance is situated between The generally higher thermal capacity of matter, it is generally preferred that liquid heat conveyance media, the medium very preferably evaporated in hot plate, At hot plate, due to the vaporization enthalpy of additional needs, the reaction controlling of even more isothermal is possible.
Preferably, the regional of reaction compartment is adiabatically operated, wherein can further increase conversion.
Finally, one embodiment of the present of invention is：The technique performed in the reactor according to the present invention is at least partly Propylene is converted methanol into, the technique represents the typical reaction in fixed bed, arranged with previous reactor, this reaction needs Very big reactor with disadvantages associated.
Further characteristic of the invention, advantage and possible application can be obtained from the following explanation to accompanying drawing and example. Described and/or shown all features are all referred to independently in itself with their inclusions in the claims or the inverse of them Or with any combinations formation subject of the present invention.
Brief description of the drawings
In the accompanying drawings：
Fig. 1 shows the construction of traditional multistage fixed bed reactor,
Fig. 2 shows the construction of the reactor according to the present invention, and
Fig. 3 a and Fig. 3 b show the construction of used hot plate.
Reference numerals list：
10 according to the reactor of prior art
111-116Fixed bed
121-126Heat exchanger
13、131-136Methanol feed conduit
14 products discharge conduit
20 according to reactor of the invention
21 adiabatic regions
22 feed conduits
23 distributor chambers
241-247Heat transmission space
24D passage openings
251-256Reaction compartment
26 discharge conduits
27 holding meanss
28 remove device
30 hot plates
30a, 30b plate
311-319Solder joint
321、322Heat transfer channel
Embodiment
Fig. 1 is discussed on prior art.
Fig. 2 is presently shown the reactor 20 according to the present invention.Via feed conduit 22, educt such as methanol is introduced into point With in room 23.Multiple openings are (such as towards the slit in reactor 20) from this branch of distributor chamber 23.Distributor chamber 23 can be by It is directly placed on reactor 20, or an even part for reactor 20, and for example formed by protuberance.However, also will Distance between opening and real reaction area is selected, so that uniform flow is close to reaction zone.
Meanwhile, also it is possible that reaction medium is introduced into reactor 20 in a not shown manner via nozzle.Nozzle in Be be arranged such that ensure it is uniform through-flow.
Reaction compartment 251To 256By Heat transmission space 241To 247Limit, Heat transmission space 241To 247By at least one heat Plate shape into.As indicated, reaction compartment 251To 256It is at least partially filled with catalyst, reaction medium such as methanol energy It is enough to be converted on a catalyst.
Obtained product stream is extracted via conduit 26.
Two adjacent heat transmission spaces 24nTo 24n+1The distance between each limit the reaction compartment with width d1 25m.It is arranged such that：Reaction medium is first vertically from top to the reacted space 25 of underflow1To 256, and in lower adiabatic region 21 In, reaction compartment is not by each Heat transmission space 241To 247Separate each other.In this region 21, reaction is adiabatically carried out, because For no heat dissipation or heat supply.In Heat transmission space 241To 247Region in, nearly quasi-isothermal reaction controlling can be taken. Heat exchanger plate 241To 247Each also has at least one unshowned entrance and exit.Also it is possible that：With not shown Mode Heat transmission space top provide catalyst, and thus extend reaction compartment.
Catalyst is shelved at least one holding means 27 such as appropriate grid.This holding meanss 27 can It is shifted or discharges via removal device 28, so that catalyst is fallen and easily can be moved at the bottom of reactor 20 Remove.
Fig. 3 a show the x-y views on the surface of the plate in the side for forming hot plate on hot plate 30.Point 311To 319Represent By the so-called solder joint of additional spot welding, the plate is set to be connected with the unshowned plate on opposite side by these solder joints.Point 311Extremely 313、314To 316With 317To 319Each is respectively positioned on straight line, and the point of each of which second straight line is all again alternately with phase The other sizes answered are located on straight line.These straight lines are extended parallel to each other and with apart from d5.
Because hot plate is not only welded together in the edge of two overlapping plates, and additional bond-pads 311To 319Also position In on hot plate, so obtaining section expression figure as shown in figure 3b in the x-z views through hot plate.In each spot welding 311 To 319Between formed passage 321With 322, passage is generally produced by pressure forming (being particularly preferably molded by internal high pressure) 321With 322.Such passage 321Or 322Diameter d2 describe between the two boards 30a and 30b of largest passages form away from From, and diameter d4 indicates solder joint 311To 319Thickness.Two solder joints 311To 319The distance between (also correspond exactly to Two solder joints 31 on one straight line1To 319Distance) correspond to d3.Preferably, using following relationship：d3>d2>d4.
Exemplary embodiment
Example 1
Example 1 show reactor design in as shown in Figure 1 according to the reactor of prior art compared with according to this hair The bright difference for being designed to reactor in the horizontal plane for annular.According to the data of the reactor of prior art, each is equal Represent, and represented in relation according to the reactor of the present invention with 100%.
Table 1：According to the reactor of prior art and according to the present invention reactor physical dimension comparison.
Transverse cross-sectional area in horizontal plane can be filled to be circle, but also can be certainly any other shape.Certainly It is qualitatively：The shape of reactor provides the good distribution of reaction medium and being easily processed for catalyst.
It should be appreciated that being significantly reduced according to the size of the reactor of the present invention, because due to local heat dissipation, finally can Omit very big heat exchanger.Almost three times of the ratio increase of catalyst and reactor volume.Therefore, according to the anti-of the present invention The space-time yield in device is answered to significantly improve.
Example 2
With reference to passing throughThe simulation of execution, example 2 is shown by the improvement reaction controlling closer to isothermal operation The Propylene Selectivity increase at least 2% in the reactor according to the present invention can be made.This with the whole flowing road of reaction medium The fact that there is the much smaller temperature difference on footpath is related.According to the data of the reactor of prior art, each is represented with 100%, And represented in relation according to the reactor of the present invention.
Table 2：According to the reactor of prior art and according to the present invention reactor physical dimension comparison.
Parameter Prior art According to the reactor of the present invention
Catalyst weight (t) 150 150
Total catalyst bed height (m) 100% 100%
Total moisture content raises (K) 100% About 15%
Heat dissipation (MW) 100% 100%
The pressure loss on reactor 100% About 70%
The pressure (bar) of the reactant mixture in exit 100% 100%
The temperature (DEG C) of the reactant mixture in exit 480℃ 480℃
Propylene Selectivity (mol C-%) 65 >67
Table 3 shows to depend on the productivity of propylene with the temperature deviation of ideal response temperature.
And the mean temperature deviation (K) of optimal reaction temperature 15 10 5 2.5 0
Propylene Selectivity (mol C-%) 65 67 68 68.5 69
Common response device system shows about 15K deviation, thus productivity of propylene is 65mol C-%.For with optimum response The mean temperature deviation of temperature, this new reaction device system will be in the range of 10 to 0K, preferably in the range of 2.5 to 0K.Therefore Significantly improve the yield of propylene.

Claims (15)

1. a kind of reactor (20), the reactor (20) is used for at least two reaction compartments (251To 256) reformed gas and/ Or liquid reaction medium, at least two reaction compartment (251To 256) it is at least partially filled with catalyst, the reactor It is formed to be disposed with least three Heat transmission spaces (24 of arrangement substantially parallel to one another in the reactor (20)1Extremely 247), the Heat transmission space is thus at least in part by each reaction compartment (251To 256) separate each other, wherein the heat is passed Defeated space (241To 247) each by least one hot plate (30) formation, each of which hot plate (30) by two boards (30a, 30b) constitute, the two boards (30a, 30b) are connected to each other at multiple other positions of edge and surface, its It is characterised by operation, the reactor (20) horizontal-extending at least one axis is more than the reactor (20) Vertical extension, and entrance (22) and the outlet (27) of the reaction medium are provided for, so as to the reactor (20) quilt The reaction medium is vertically crossed.
2. reactor (20) according to claim 1, it is characterised in that the reaction compartment (251To 256) vertically extend More than the Heat transmission space (241To 247) the extension.
3. reactor (20) according to claim 1 or 2, it is characterised in that it is described that the plate (30a, 30b) is connected Other position is located on straight line, wherein each position (311To 319) each other point-blank be all the time apart from each Same distance d3, and wherein described straight line has same distance d5 all the time each other.
4. the reactor (20) according to any one of preceding claims, it is characterised in that：In the position (311Extremely 319) between, the hot plate (30) has cushion passage (321、322), wherein the two boards (30a, 30b) it is mutual it is maximum away from From being distance d2, and the distance between two adjacent hot plates (25) d1 is more than d2, and described is less than the distance apart from d1 100 times of d2.
5. reactor (20) according to claim 4, it is characterised in that it is described apart from d1 be in 1.5*d2 and 10*d2 it Between, and/or it is described apart from d3 be more than it is described apart from d2.
6. the reactor (20) according to any one of preceding claims, it is characterised in that be provided for the catalyst Removal device (28).
7. the reactor (20) according to any one of preceding claims, it is characterised in that the Heat transmission space (241 To 247) be designed to guide fused salt, and wherein described Heat transmission space (241To 247) be arranged such that：When the equipment During shutdown, the hot plate (30) is emptied by gravity.
8. the reactor (20) according to any one of preceding claims, it is characterised in that the reaction compartment (251Extremely 256) catalyst bed will be filled with, wherein for every m3Catalyst bed, the reactor (20) include at least one hot plate (30), and/or per m3Catalyst bed have at least 10m2Cooling surface.
9. the reactor (20) according to any one of preceding claims, it is characterised in that empty at least one Heat transmission Between in, from a reaction compartment (251To 257) additional via opening (24 is set to another reaction compartmentD)。
10. the reactor (20) according to any one of preceding claims, it is characterised in that reactor (20) bag Gas distributing device (23) is included, the reaction medium is uniformly distributed in all reaction compartments by the gas distributing device (23) (251To 256) on.
11. a kind of be used for the technique with least two reaction compartment reformed gas and/or liquid reaction medium, described at least two Reaction compartment is at least partially filled with catalyst, wherein the reaction medium flows through each reaction compartment, wherein the reaction Space is formed by least three Heat transmission spaces of arrangement substantially parallel to one another, and wherein heat transport medium to flow through each equal The Heat transmission space formed by least one hot plate, each of which hot plate is made up of two boards, and the two boards are on side It is connected to each other at multiple other positions of at edge and surface, it is characterised in that the reaction medium vertically flows through institute Reactor is stated, wherein the horizontal-extending vertical extension more than the reactor at least one axis of the reactor.
12. technique according to claim 11, it is characterised in that the heat transport medium by with cocurrent or with adverse current or Person is guided to the reaction medium with cross-current.
13. technique according to claim 11, it is characterised in that each of the heat transport medium in the hot plate All it is liquid at position, or is evaporated in the hot plate.
14. the technique according to any one of claim 11 to 13, it is characterised in that each reaction compartment is partly exhausted Heat operation.
15. the technique according to any one of claim 11 to 14, it is characterised in that oxide is turned at least in part Turn to propylene.
CN201611175285.8A 2015-12-17 2016-12-19 Reactor for performing heat release or the endothermic reaction Pending CN106955645A (en)

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