CN100381200C - Electrically heated reactor and process for carrying out gas reactions at a high temperature using this reactor - Google Patents
Electrically heated reactor and process for carrying out gas reactions at a high temperature using this reactor Download PDFInfo
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- CN100381200C CN100381200C CNB2004800100288A CN200480010028A CN100381200C CN 100381200 C CN100381200 C CN 100381200C CN B2004800100288 A CNB2004800100288 A CN B2004800100288A CN 200480010028 A CN200480010028 A CN 200480010028A CN 100381200 C CN100381200 C CN 100381200C
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/02—Preparation, separation or purification of hydrogen cyanide
- C01C3/0208—Preparation in gaseous phase
- C01C3/0229—Preparation in gaseous phase from hydrocarbons and ammonia in the absence of oxygen, e.g. HMA-process
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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
- B01J19/2485—Monolithic reactors
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00018—Construction aspects
- B01J2219/0002—Plants assembled from modules joined together
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00094—Jackets
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00132—Controlling the temperature using electric heating or cooling elements
- B01J2219/00135—Electric resistance heaters
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/085—Methods of heating the process for making hydrogen or synthesis gas by electric heating
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
- C01B2203/1023—Catalysts in the form of a monolith or honeycomb
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
Abstract
The invention relates to an electrically heated reactor (1) for carrying out gas reactions at a high temperature. The reactor comprises a reactor block (2), of one or more monolithic modules (3) of a material which is suitable for an electrical heating, surrounded by a casing (10 to 13), channels (4) extending through the module(s) and being constructed as reaction channels, and a device for passing through or inducing a current in the reactor block. The safety during operation of such a reactor is increased according to the invention in that the casing of the reactor block comprises a double-walled jacket (13) which seals this off gas-tight, and at least one device (14) for feeding an inert gas into the double-walled jacket. The invention also provides a process for carrying out gas reactions at a high temperature, such as the BMA process for the preparation of hydrogen cyanide, using the reactor.
Description
Technical field
The present invention relates to a kind of being used at high temperature, particularly temperature is higher than under 500 degrees centigrade, finish the electrically heated reactor of gas reaction, described reactor comprises the reactor block of one or more channelled monolithic modules, this passage is constructed to reaction compartment, and realizes heating by resistance heated or eddy-current heating.
The present invention relates to a method of using this reactor at high temperature to finish gas reaction, particularly heat absorptivity gas reaction simultaneously.
Background technology
As everyone knows, various reactors be used at high temperature finishing occur in that catalyst exists or the shortage situation under in the reaction of gaseous state, normally heat absorptivity gaseous state reaction.Except other difference, the difference between these reactors is also how energy is fed to the gas or the admixture of gas that will react, for example by the heat that produced by direct or indirect path inflammable gas burning or pass through electric energy.
DE 35 33 385 C1 disclose a kind of baking oven that is used for finishing the tubulose of gas reaction, and be used in particular for preparing hydrogen cyanide by BMA technology: the tubulose baking oven comprises the heating chamber of brickwork lining cutting, wherein is furnished with the earthenware as reaction compartment.In order to heat, electrical heating elements is set to and manages parallelly, and in addition, the chamber comprises inside and outside radiant walls.Heating element heater is made by the material that is suitable for resistance heated.The topmost defective of this tubulose baking oven is its labyrinth and fragility, because reaction tube and heating element heater all may break and therefore cause device to be stopped work.
In the effort that reduces heat absorptivity gas reaction institute energy requirement, DE 196 53 991 A1 propose to use and comprise heat tunnel and the monolithic reversing the current reactor of the reaction channel of the extension that is parallel to each other.Can not obtain to construct the monolithic reactor so that the suggestion of the current flow heats that monolithic (monolith) is passed through by this document.
EP 0 684 071 A1 disclose a kind of monolithic body, and it has electrical heating activated charcoal structure and is used to make the fluid product stream device of monolithic (monolith) passage of flowing through.In this reactor, be arranged on the insulation monolithic inorganic substances by continuous unbroken activated charcoal layer, particularly ceramic honeycomb structural body by current flow heats.In a relative side, it is structural as the conductive material of electrodes band that this structure is included in activated charcoal.This reactor can be used to the method for from fluid product stream absorption or desorption composition.The document particularly points out, if the medium of flowing through is not an inertia, then the monolithic reactor is the highest 350 degrees centigrade of operations down.According to the principle of the document, if gas reaction will carried out under the high-temperature very much, for example be higher than the BMA technology of carrying out under 1000 degrees centigrade, it is impossible then using this reactor.A problem of this reactor is that obviously coating will come off along with the frequent variation of temperature.How to find in this document this reactor redesign so that it can carry out the suggestion of the gas reaction that need finish safely under high-temperature very.
GB patent specification 1 238 468 discloses the another kind heating type of the reactor that is used to finish the gas reaction that need carry out under high-temperature very: two electrodes relatively are arranged in the case shape reactor, in order to heat the catalyst bed that electric current is made by the conductive material that is arranged in the reactor.Principle among WO 02/45837 A2 is similar fixed bed reactors, and this reactor has two electrodes, and one is positioned at another inside and concentric with it, and the fixed bed that conductive material is made is arranged between the electrode, and fluid can flow by fixed bed.BMA technology and reforming method are mentioned as the use field.Though in this container, can finish gas reaction with satisfactory way below 900 degrees centigrade with the fixed bed that is suitable for resistance heated, but under higher temperature and particularly have in the reaction that hydrogen exists, problem constantly occurs: if advise as the document, fixed bed comprises the mixture of conduction and insulation or semi-conducting material, will take place to flow in the electric current conduction.
According to WO 95/21126, a kind ofly also can pass through eddy-current heating by the granuloplastic catalyst fixed bed reactor that is used for gaseous state reaction under the situation that exists.In this application, owing to expense, also have higher technical fee, so eddy-current heating is less preferred except required protector.
According to NL Patent 121 661, preferably in the presence of diluent gas, for example hydrogen if react, under 1600 to 2500 degrees centigrade, can be made hydrogen cyanide by ammonia and methane in the tubular graphene reactor.Required reaction temperature realizes by the graphite-pipe resistance heated.Graphite-pipe one end to the other end insulate, and is encased by the external conductive casing that links to each other with pipe.The technical difficulty that is caused by very high running temperature makes that this method is not very attractive for integrated mill.
At the WO 96/15983 described reactor that is used for preparing by BMA technology hydrogen cyanide, institute's energy requirement is equally by by graphite or have reaction tube resistance heated or the eddy-current heating made as the graphite block in the hole of reaction channel and realize.Except graphite, the coating that also can use other conductive materials or these materials to make.In addition, reaction tube or hole can scribble catalyst coating.The oxidized aluminum fiber insulating barrier of reactor block and the steel reaction outer wall that comprise reaction tube or reaction channel surround.When this reactor was used for preparing hydrogen cyanide from methane and ammonia, the owner of protection right was further running into sizable safety-related problem in the operation reactor process.Disclosed this device correspondingly must be done improvement to realize the possible safety in production of hydrogen cyanide in it aspect several at present.
Other one group of electrically heated reactor is based on the plasma that generates in the reactor.Because high technical fee, this reactor does not almost have attraction to large-scale industrial application.Therefore the reactor and the method for the plasma that generation heated air medium is used are no longer further considered, and are excluded outside theme protection domain of the present invention.
Summary of the invention
The purpose of this invention is to provide a kind of improved electrically heated reactor, be used at high temperature finishing safely gas reaction, particularly be higher than 500 degrees centigrade, and preferably be higher than under 900 degrees centigrade of ground temperature, the defective of above-mentioned known reactor is overcome at least on one point.
The another one purpose relates to provides a kind of reactor with reaction compartment of passage shape, and it can be under the situation that hydrogen exists as reacted constituent, safe operation when being higher than 900 degrees centigrade.
Another purpose provides a kind of general type reactor with simple structure, and this reactor is not fragile and can be modified to have desirable production capacity by simple mode.
According to the preferred embodiment of reactor of the present invention, this reactor should be readily incorporated into the equipment that is used for finishing gas reaction, and this reaction purpose is for obtaining the generation of reacting gas and these gases.If except desirable reacting gas (for example hydrogen cyanide), hydrogen additionally forms gas in gas reaction, this reactor should be attached in this device so that hydrogen can be used in the combined system to rise to the benefit of the method that obtains reacting gas.
The application's inventor finds, with respect to those reactors that in thick close sintered ceramic reaction tube, carries out gas reaction, for example safety problem can appear in the reactor of the conductive material of graphite, and this is because this material and other known materials that are used for resistance heated are not fully airtight.Owing to arrange that the reactor heat-insulating material on every side of operation at high temperature is not airtight usually equally, if the therefore destroyed or not suitably sealing of shell of reactor, then dangerous situation may take place.
Have been found that the problems referred to above can solve by simple mode, be about to shell of reactor and be configured to the double-walled big envelope, be filled with inert gas therebetween, or preferably, inert gas passes this big envelope and flows.By the lasting analysis that the inert gas of the double-walled big envelope of flowing through is formed, it is destroyed and air is entered to understand fully immediately that gas that reaction compartment discharges enters double-walled big envelope or the double-walled big envelope outside.In case the inert gas composition between the double-walled big envelope changes, the expert will take measures necessary to avoid occurring unsafe precarious position.
Have been found that a kind of electrically heated reactor that is used at high temperature finishing gas reaction, it comprise surrounded by shell by being suitable for the reactor block that one or more monolithic module constituted that resistance heated or eddy-current heating material are made, extend to the passage that is configured to reaction compartment of a relative end from reactor block one end, the device that is used for gas medium in passage is introduced gas medium or passing away under every kind of situation, and at least two be connected in be used on power supply and the reactor block transmission current by reactor block electrode or introduce the device of electric current to reactor block, it is characterized in that:
The shell of reactor block comprises makes its air-locked double-walled big envelope, this double-walled big envelope have at least one is used for introducing inert gas between the double-walled big envelope device the reactor block sealing.
The dependent claims of this electrically heated reactor wherein relates to preferred embodiment and comprises the device of having integrated this reactor.Particularly preferably, the double-walled big envelope has and is used to introduce the device of inert gas and the device that same gas is discharged in other being used to, like this inert gas double-walled big envelope of can flowing through.
Description of drawings
The present invention will be by being described in detail with reference to figure 1-4:
Fig. 1 shows the cutaway view pass electrically heated reactor, and this reactor has the reactor block that comprises four monolithic modules, and according to the multilayer package that the present invention includes the double-walled big envelope, inert gas this double-walled big envelope of flowing through.
Fig. 2 is that the longitudinal sectional view of reactor block is passed in demonstration, and this reactor block has eight monolithic modules, and the passage that is configured to reaction compartment is arranged parallel to each other, and every passage passes all component and extends.
Fig. 3 shows to pass the cutaway view of monolithic module, and has represented the vertically extending reaction channel with figure.
Fig. 4 is the pattern that has shown a kind of device, in this device, the gaseous matter of sending into reacts in reactor according to the present invention, a kind of precious material of reacting gas is converted into a kind of second product, another precious material that is called inflammable gas separates from residual gas and then burns in fuel unit, and thus obtained electric current is used for heating according to reactor of the present invention.
The specific embodiment
Reactor shown in Figure 1 comprises by a plurality of monolithic modules 3 and stacks the reactor block 2 that constitutes on it mutually that a plurality of parallel reaction passages 4 pass this reactor block and extend.Reactor block can comprise one or more monolithic modules, but as illustrated in fig. 1 and 2, particularly preferably comprises a plurality of monolithic modules that stack mutually on it, and reaction channel passes all assemblies and extends.The component count that stacks mutually depends on gas or admixture of gas react required lasting time and the predetermined capacity of reactor.By increasing one or more assemblies to reactor block, improve the gas flow speed that will react simultaneously, can increase the capacity of reactor.
In principle, stack on it mutually or a plurality of assemblies that are arranged side by side of being parallel to each other can be used for structure and form reactor block.The cross-sectional view of assembly can be in fact arbitrarily.Cross section is that circle, rectangle or hexagonal assembly are all suitable especially.The height of single component equally also can be selected arbitrarily.Under the situation of selecting circular components, the ratio between diameter and the height is usually between 0.5 to 5, preferably between 1 to 4.
Each monolithic module comprises at least one reaction channel, but preferably includes a plurality ofly, and reaction channel extends to a relative side from a side of assembly.Passage preferably is arranged to be arranged in parallel with each other.Yet another kind of arrangement mode is not left out yet, the arrangement mode that for example a plurality of pipes extend with certain angle mutually.
Wherein a plurality ofly has the assembly of same structure according to a kind of by embodiment stacked one on top of the other, by for example alignment pin 16 or meet tongue-and-groove and pass in principle, thereby can realize the center and realize that passage 4 is communicated with the special design of fringe region up and down of each assembly of engaging with another assembly.In order to guarantee between the single component as far as possible evenly and flatly contact that the dividing surface that stacks mutually should be configured to smooth as much as possible.
According to alternative a kind of embodiment of reactor block, stack directly contact between the assembly of arrangement mutually, but by the seal between assembly.The sealing part can be conduction or insulation, and is configured to so that the admixture of gas of discharging in the passage of first assembly can enter the passage of second assembly that is positioned at opposite face.For example, seal is configured to so that have on it and the corresponding to hole of assembly.According to a kind of alternative mode, seal is configured to the cover layer between two assemblies.For example can by in suspension media for example graphite granule or/and the minimum slurry of the preferably particle of metallic particles should be used for making conductive covering layer.Suitable metallic particles is made by the element of the subgroup of the 8th family on the periodic table of elements for example and first family and the alloy formed thus.Seal suitably has the fusing point that is higher than its operating temperature.Be coated with upper caldding layer and, suspension media evaporated by heating with after the mutual stacked arrangement of each assembly.
For the preferred resistance heated of realization response device piece, be arranged on the opposite side by the electrode 8 and 8 ' that passes through supply lines 9 power supplies of appropriate structuring.In the embodiment shown in fig. 1, monolithic module stacks gradually over each other, thereby electric current is by all assembly reactor heating pieces like this.If assembly has circular cross section, the top and the bottom that electrode are arranged on assembly are very favourable, and electrode is configured to annular or has the form of the dish type of access portal.Have at assembly under the situation of rectangular cross section, construct electrode with dish-like form usually.Electrode must with closely contact with the respective surfaces of its contacted assembly.This is attainable, for example the weight by spring or several assemblies itself of stacking mutually form the pressure contact.For guaranteeing better contact, it is favourable that the cover layer that layer of conductive material makes is set between electrode and the assembly that is in contact with it.If reactor block is by a plurality of assembly structures and insulating sealer is set between assembly, then each monolithic module must be equipped with corresponding electrode and supply lines or have suitable connector between first assembly and adjacent component.In the embodiment that a kind of independent assembly or assembly group are powered, may in reactor block, form specific Temperature Distribution.
This electrode is made by the electrode material with high heat stability habitual in the technical field easily, for example electrode graphite.
Selection particular importance for the monolithic module material.By to can be same substance or mixture the selection of material, the assembly that can obtain to have this specific electrical resistance can easily obtain predetermined reaction temperature by the Ohmic resistance heating thus.Therefore, assembly is made by the conductive material with specific electrical resistance, this specific electrical resistance greater than 1 μ Ω m up to or even surpass 1000 μ Ω m, particularly greater than 10 μ Ω m, and preferably between 15 to 100 μ Ω m.Described specific electrical resistance relates to whole material.Because the effective cross section reduces, the specific resistance of this assembly increases along with the increase of number of active lanes.
Be used as carbide and the nitride of the suitable material of assembly for for example graphite, carbon black, carbide and nitride, particularly silicon and titanium.By these materials are mixed with non-conductive or semi-conducting material, if mixture is very even and abundant sintering together, can further improve specific resistance.
Reactor block is almost completely surrounded by the shell of while as heat insulator.This heat insulator comprises one or more layers, and the selection of heat insulation layer material depends on predetermined temperature range.In the embodiment shown in Figure 1 that provides by example, reactor block has three layers of shell, i.e. heat insulation layer 1,2 and 3 (10,11,12).The material of heat insulation layer and the selection of thickness depend on the coefficient of expansion and the interior predetermined Temperature Distribution of heat insulator of selected materials.According to a preferred embodiment, insulating barrier 1 is a flexible material, and the fibrage made of graphite fibre or non-weaving mineral fibres or these materials for example is by these materials, can include the coefficient of expansion of reactor block and heat insulation layer 2 in consideration, therefore fracture phenomena can not take place. Heat insulation layer 2 and 3 can be made by known heat insulator, comprises lightweight building stones and vacuum forming building stones.Be used for inlet side and outlet one side that radiation proof device 7 and 7 ' is arranged at the reactor block passage easily.
To the element of the requisite reactor of the present invention is that the shell of reactor block has a double-walled big envelope of being made by gas impermeable material, makes its sealing air tight.This double-walled big envelope 13 has at least one device 14 that is used to introduce inert gas, and preferably has the device 15 that another one is used to discharge same gas.These devices are arranged on the double-walled big envelope so that the inner constant compression force that keeps of double-walled big envelope perhaps makes even the flowing of inert gas pass whole double-walled big envelope.The double-walled big envelope not necessarily must be set in place on following heat insulation layer with as the outermost wall of reactor, but also can be arranged between the two-layer heat insulation layer.
Have been found that the material that is commonly used to make assembly is not fully airtight, so the sidewall leakage that gas can pass assembly goes out.If gas or admixture of gas comprise inflammable and/or toxic gas, the leakage of gas means sizable danger.Because reactor according to the present invention is designed to finish the gas reaction of gas reaction, particularly heat absorptivity, reforming method and be used to prepare the BMA technology of hydrogen cyanide for example, reacting gas comprises hydrogen simultaneously.Because be commonly used to make the void porosity that the material of reactor block lagging casing has height, these materials neither be airtight.Therefore, double-walled big envelope one side according to the present invention is as diffusion barrier, improved the security of equipment on the other hand, even because the outer wall of double-walled big envelope destroys, airborne oxygen can not directly contact and generate a kind of explosion hazard gases mixture with the reacting gas that passes heat insulation layer.
According to a preferred embodiment of the present invention, the component of the inert gas of discharging from the double-walled big envelope is subjected to continuous monitoring, though like this destruction that is subjected to of double-walled big envelope---be inwall or outer wall---can be detected, and can take adequate measures to avoid destroying.The safer running of reactor can realize by feature according to the present invention.Except inert gas flows is passed the double-walled big envelope, also can under the pressure that raises or reduce, remain in the double-walled big envelope and monitoring pressure inert gas.Owing to can't determine directly that double-walled big envelope inwall still is that outer wall is damaged in such an embodiment actually, therefore this embodiment is less preferred.
According to another embodiment of this reactor, the gas diffusion barriers of being made by gastight material directly is arranged on the reactor block or is arranged on of additional thermal insulation layer of inboard shell.Can realize higher security by such gas diffusion barriers, this gas diffusion barriers can be the metal shell of sealing or the coating of sealing.
According to a kind of certain embodiments, double-walled big envelope according to the present invention is configured to, and the outermost wall that makes inwall have the function of gas diffusion barriers and reactor also is the outer wall of double-walled big envelope simultaneously.
Monolithic module generally includes many continuous passages.According to a kind of particularly preferred embodiment, the diameter range of passage is between 2 to 20mm, preferably between 3 to 10mm.Very Duo passage can be arranged in the narrow space, and uses the space/time income of the gas reaction that this reactor finishes all very high in each case, and this is the advantage according to reactor of the present invention.Known reactor is to finish reaction in earthenware, heats by the burning of electric power or inflammable gas, and this reactor has quite low space/time income.
If gas reaction will be finished under the situation that catalyst exists, be that to be coated with the last layer coating be very favorable for the passage of assembly with active catalyst.Employed catalyst depends on predetermined gas reaction.In reforming method, correspondingly preferably use oxidiferous catalyst, in the BMA technology that is used for preparing hydrogen cyanide, can use the catalyst in the series that the nitride of the light metal that comes free platinum, platinum compounds, platinum alloy and particularly aluminium nitride forms, nitride also can form at the scene by the nitrogen that forms from ammonia in corresponding metal and the reaction.
Be used for comprising for example 4-10 assembly that stacks mutually on it with the reactor of commercial scale operation BMA technology, the high 25cm of this assembly, diameter 46cm has the hole (=passage) of 2200 diameter 5mm on it.
Except high space/time income, reactor another one advantage according to the present invention is that reactor block has simple structure and do not comprise frangible independent earthenware.
The present invention relates to a kind of device that is used to prepare also and then handles gas simultaneously, and except reactor according to the present invention, this device comprises the device that is used for producing (work up) reacting gas in addition.This device comprises heat exchanger simultaneously, the reacting gas preheating that the gas that is used or admixture of gas were discharged by reactor before entering reactor.The structure of heat exchanger meets regeneration or recyclable principle.
The device that is used for reaction of formation gas depends on constituent wherein and the target product of the precious material that generated by the reacting gas independent element fatefully.If reactor according to the present invention is used to finish the BMA technology of preparation hydrogen cyanide, be used for generating and and then the device of processing reaction admixture of gas be included in aqueous medium and absorb hydrogen cyanide or concentrated hydrogen cyanide.By the hydrogen cyanide in the absorption reaction gas in alkalinous metal or alkaline earth metal hydroxide solution, can obtain alkalinous metal cyanide or alkaline-earth metal cyanide solution, for example, particularly nacn or cyanogas solution, this in mining industry for being very common in the filter method that obtains gold.Absorb after the hydrogen cyanide, be left mainly to comprise the gas of hydrogen, this gas can directly or through further purifying the back be used as other purposes, comprises the fuel unit that is used to provide electric power.Under the situation of reacting gas compression, the method that is widely known by the people by itself can obtain to can be used for preparing the liquid hydrogen cyanide of the second other product.
Fig. 4 has represented a kind of device that has above-mentioned feature and be suitable for finishing BMA technology in a kind of special mode.This device comprises according to reactor 1 of the present invention, is used for the heat exchanger 17 of the gas 18,19 that preheating is used to react, and the pipeline 20 that is used for the mixture of preheating gas that reacts at reactor.The reacting gas that leaves reactor by pipeline 21 inflow heat exchangers 1 with release portion heat there.The reacting gas that is partly cooled off flows into generating apparatus 23 by pipeline 22.Be used to generate required auxiliary substance, for example alkalinous metal or the alkaline-earth metal cyanide solution under the situation of preparation alkalinous metal or alkaline-earth metal cyanide from the reacting gas that comprises HCN is admitted to by pipeline 25.The reactor product that comprises hydrogen cyanide that reacting gas generates, promptly alkalinous metal cyanide or alkaline-earth metal cyanide solution or liquid hydrogen cyanide are discharged from system by pipeline 24.Residual main component is that the gas of hydrogen is divided into hydrogen stream 28 and residual gas stream 29 by the device 27 that is used for Purge gas from generating apparatus.The hydrogen stream that process purifies flows into fuel unit 30, and burning therein generates water, and the water of generation can enter generation section 23 by pipeline 31 and be recycled.The electric power that produces in the fuel unit is transported to electrically heated reactor by lead 32.In illustrated closed-system, finish the required most of energy of heat absorptivity gas reaction and burn in fuel unit by hydrogen and obtain.When particularly the hydrogen that produces as byproduct did not have other possible purposes, this embodiment was favourable.
As mentioned above,, particularly be higher than 500 degree, more especially be higher than 900 degree down, the endothermic reactions of carrying out according to reactor of the present invention and comprise that the device of this reactor can be used to finish the gas reaction method of carrying out under the high temperature.If gas reaction is pure pyrolytic, gas that is decomposed or the admixture of gas that comprises this gas are admitted to this reactor.Under the situation of the gas reaction that at least two kinds of gases react to each other, the gas that will react is admitted to reactor at least, and if necessary, admixture of gas can comprise those in addition and be inert gasses under reaction condition.This method can be carried out under active catalyst existence or non-existent situation, and this depends on reaction type.
A kind of special preferred embodiment of the method according to this invention, ammoniacal liquor and lower carbon number hydrocarbons, particularly methane, under 1100 to 1200 degrees centigrade, reaction produces hydrogen cyanide and hydrogen under the suitable catalyst action that is used for BMA technology.
An other method relates to reforming method, and wherein for example the inflammability material of methyl alcohol is converted into hydrogen and carbon dioxide (CO under there is situation in steam
2), and hydrogen can be sent into fuel unit to obtain electric energy.
Reference identification
1 reactor
2 reactor block
3 monolithic modules
4 passages (reaction compartment)
5 air inlets (admixture of gas that reacts)
6 exhaust outlets (reactant mixture)
77 ' radioprotector
88 ' electrode (annular)
9 supply lines
10 heat insulation layers 1
11 heat insulation layers 2
12 heat insulation layers 3
13 tank walls (double-walled big envelope)
14 inert gas air inlets
15 inert gas exhaust outlets
16 alignment pins
17 heat exchangers
18 air inlets (gas 1)
19 air inlets (gas 2)
20 admixture of gas floss holes
21 enter 17 reacting gas pipeline
22 from 17 gas pipelines of drawing
23 generating apparatus
24 auxiliary substance charging apertures
25 reactor product outlets
26 lead to the pipeline of device 27
27 gas fractionation units
28 combustion pipes (hydrogen)
29 residual gas floss holes
30 fuel units
31 water pipes
32 fuel units are to the supply lines of reactor
Claims (21)
1. be used at high temperature finishing the electrically heated reactor (1) of gas reaction, comprise: reactor block (2), one or more monolithic modules (3) that described reactor block is made by the material that is suitable for resistance heated or eddy-current heating are formed, and described reactor block is centered on by shell (10 to 13); What be configured to reaction compartment extends to the passage of a relative side from reactor block one side; Be used for introducing and from passage, discharging the device of gas medium (5 and 6) in each case to passage; And at least two be connected in be used on power supply and the reactor block to make electric current by reactor block electrode (8,8 ') or produce the device of electric current at the reactor block internal induction, it is characterized in that:
The shell of reactor block comprises that the double-walled big envelope (13) that makes its sealed air-tight and at least one are used for introducing the device (14) of inert gas in the double-walled big envelope.
2. electrically heated reactor as claimed in claim 1 is characterized in that:
The double-walled big envelope has the device (15) of discharging inert gas.
3. electrically heated reactor as claimed in claim 2 is characterized in that: the described device that is used to discharge inert gas is connected to gas analyzing apparatus
4. as the described electrically heated reactor of one of claim 1-3, it is characterized in that:
Reactor block comprise a plurality of each other directly or at interval overlay on another or the monolithic module of side by side layout in a distance ground by seal, and passage is arranged so that can flow through all component and from the relative side discharge of reactor block of the gas medium that infeeds from reactor block one side.
5. as each described electrically heated reactor among the claim 1-3, it is characterized in that:
Be provided with the seal that electrically insulating material is made between the assembly, the channel outlet of first assembly has corresponding access portal facing to the inlet and the seal that close on assembly.
6. electrically heated reactor as claimed in claim 5 is characterized in that:
Each heating component has the electrode of two transmission currents.
7. as each described electrically heated reactor among the claim 1-3, it is characterized in that:
Lagging casing comprises one or more heat insulation layers and gas diffusion barriers.
8. electrically heated reactor as claimed in claim 7 is characterized in that:
Gas diffusion barriers is air-locked coating or thick close sintered ceramic or vitreous material.
9. as each described electrically heated reactor among the claim 1-3, it is characterized in that:
Assembly is made by the conductive material with specific electrical resistance, and this specific electrical resistance is greater than 1 μ Ω m.
10. electrically heated reactor as claimed in claim 9 is characterized in that: described specific electrical resistance is between 15～50 μ Ω m.
11., it is characterized in that as each described electrically heated reactor among the claim 1-3:
This passage to small part has the coating of catalytic activity.
12. each described electrically heated reactor among the claim 1-3 is characterized in that:
Radioprotector (7,7 ') is arranged on the reactor block both sides, i.e. feeder connection and exit.
13., it is characterized in that as each described electrically heated reactor among the claim 1-3:
Assembly is made by insulation graphite and electrode is made by electrode graphite, and wherein said electrode is a circular structure, or constructs and adopt the dish type structure in the dish type that adopts perforation under the cylindrical assembly situation under the parallelepiped assembly situation.
14., it is characterized in that as each described electrically heated reactor among the claim 1-3:
This reactor is incorporated in the equipment, and this equipment comprises the device (23) of the gas medium (reacting gas) that is used for the generate reactor discharge and is used for being connected to by gas pipeline (21) device of the gas medium discharge of generating apparatus.
15. electrically heated reactor as claimed in claim 1 is characterized in that:
This reactor is incorporated into one and comprises in the equipment of heat exchanger (17), and the gas medium of question response this heat exchanger of flowing through heats before entering channel of reactor at it, and flows through this heat exchanger so that cooling from the reacting gas that reactor is discharged.
16., it is characterized in that as claim 1 or 15 described electrically heated reactors:
This reactor is incorporated in the equipment, this equipment comprises the device (23) that is used to generate from the gas medium (=reacting gas) of reactor discharge, the inflammable gas (29) that is contained in this is separated, and the additional fuel unit that is used for burning combustible gases (30), this fuel unit is connected to be used for reactor heating (1) as the energy.
17. a method of at high temperature finishing gas reaction, particularly in the endothermic reaction that is higher than under 500 degrees centigrade, at least two kinds of gases that react to each other have or are lacking under the catalyst situation, through reactor, it is characterized in that under the effecting reaction temperature:
Gas reaction is finished according in one among the claim 1-16 or the multinomial described reactor.
18. method as claimed in claim 17 is characterized in that:
Gas reaction is hydrogen cyanide and hydrogen that obtains from ammoniacal liquor and lower carbon number hydrocarbons formation.
19. method as claimed in claim 18 is characterized in that: lower carbon number hydrocarbons is methane " a BMA technology ".
20. method as claimed in claim 17 is characterized in that:
This method is a reforming method, obtains hydrogen from the combustible material of for example methane.
21., it is characterized in that as claim 17 or 18 described methods:
Hydrogen separates from reacting gas, and with the air acquisition electric energy that burns, and the electric energy that is obtained is used for reactor heating in fuel unit.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10317197.5 | 2003-04-15 | ||
| DE2003117197 DE10317197A1 (en) | 2003-04-15 | 2003-04-15 | Electrically heated reactor and method for carrying out gas reactions at high temperature using this reactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1774291A CN1774291A (en) | 2006-05-17 |
| CN100381200C true CN100381200C (en) | 2008-04-16 |
Family
ID=33103379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800100288A Expired - Fee Related CN100381200C (en) | 2003-04-15 | 2004-04-02 | Electrically heated reactor and process for carrying out gas reactions at a high temperature using this reactor |
Country Status (5)
| Country | Link |
|---|---|
| CN (1) | CN100381200C (en) |
| AU (1) | AU2004229151A1 (en) |
| DE (1) | DE10317197A1 (en) |
| WO (1) | WO2004091773A1 (en) |
| ZA (1) | ZA200508311B (en) |
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| DE102005034642B3 (en) * | 2005-07-25 | 2006-08-03 | Siemens Ag | Laboratory microfluidic analytical mixer unit has two separate passage systems, one of which has internal leak detector |
| DE102005051637A1 (en) * | 2005-10-26 | 2007-05-03 | Atotech Deutschland Gmbh | Reactor system with a microstructured reactor and method for carrying out a chemical reaction in such a reactor |
| WO2013135657A1 (en) * | 2012-03-13 | 2013-09-19 | Bayer Intellectual Property Gmbh | Method for producing synthesis gas in alternating operation between two operating modes |
| WO2013135668A1 (en) | 2012-03-13 | 2013-09-19 | Bayer Intellectual Property Gmbh | Chemical reactor system, comprising an axial flow reactor with heating levels and intermediate levels |
| WO2013135660A1 (en) | 2012-03-13 | 2013-09-19 | Bayer Intellectual Property Gmbh | Axial flow reactor having heating planes and intermediate planes |
| DE102013209883A1 (en) | 2013-05-28 | 2014-12-04 | Evonik Industries Ag | Integrated system and method for the flexible use of electricity |
| DE102013209882A1 (en) | 2013-05-28 | 2014-12-04 | Evonik Industries Ag | Integrated system and method for the flexible use of electricity |
| US10337110B2 (en) | 2013-12-04 | 2019-07-02 | Covestro Deutschland Ag | Device and method for the flexible use of electricity |
| EA201990682A1 (en) * | 2016-09-13 | 2019-10-31 | DEVICE AND ITS APPLICATION FOR PRELIMINARY HEATING AT LEAST ONE ONE FLUID | |
| FI3802413T3 (en) | 2018-05-31 | 2023-08-11 | Topsoe As | Hydrogen production by steam methane reforming |
| EP3574991A1 (en) * | 2018-05-31 | 2019-12-04 | Haldor Topsøe A/S | Steam reforming heated by resistance heating |
| EP3801871A1 (en) * | 2018-05-31 | 2021-04-14 | Haldor Topsøe A/S | Endothermic reactions heated by resistance heating |
| FR3101075B1 (en) * | 2019-09-19 | 2022-07-29 | Commissariat Energie Atomique | : Catalytic fixed-bed reactor incorporating an electric heating element, Hydrogen production unit by steam reforming comprising such a reactor and an electric steam generator, associated operating method. |
| EP4038016A1 (en) * | 2019-10-01 | 2022-08-10 | Haldor Topsøe A/S | Synthesis gas on demand |
| EP4038013A1 (en) * | 2019-10-01 | 2022-08-10 | Haldor Topsøe A/S | On demand hydrogen from ammonia |
| CA3148730A1 (en) * | 2019-10-01 | 2021-04-08 | Haldor Topsoe A/S | Cyanide on demand |
| US11320206B2 (en) | 2019-10-04 | 2022-05-03 | Hamilton Sundstrand Corporation | Pressure vessel with barrier layer |
| BR112022009054A2 (en) * | 2019-11-12 | 2022-08-09 | Haldor Topsoe As | ELECTRIC STEAM CRACKER |
| DE102019130600A1 (en) * | 2019-11-13 | 2021-05-20 | Thyssenkrupp Ag | Process and device for the production of hydrogen and pyrolysis carbon from hydrocarbons |
| EP3835639B1 (en) | 2019-12-12 | 2023-08-30 | Basf Se | Gas-tight, heat permeable, ceramic and multilayer composite pipe |
| EP4081337A1 (en) * | 2019-12-23 | 2022-11-02 | Shell Internationale Research Maatschappij B.V. | Electrically heated reactor, a furnace comprising said reactor and a method for gas conversions using said reactor |
| EP3878547A1 (en) | 2020-03-13 | 2021-09-15 | Linde GmbH | Reactor and method for performing a chemical reaction |
| EP3900817A1 (en) * | 2020-04-23 | 2021-10-27 | Linde GmbH | Reactor and method for performing a chemical reaction |
| EP3900818A1 (en) * | 2020-04-23 | 2021-10-27 | Linde GmbH | Reactor and method for performing a chemical reaction |
| WO2022069726A1 (en) | 2020-10-02 | 2022-04-07 | Basf Se | Thermal integration of an electrically heated reactor |
| AT524770B1 (en) * | 2021-04-19 | 2022-09-15 | Radmat Ag | Process for converting phosphorus oxide to elemental phosphorus |
| CN117859037A (en) * | 2021-07-27 | 2024-04-09 | Sabic环球技术有限责任公司 | Electric furnace for heating a charge and related method |
| KR102573887B1 (en) * | 2021-09-10 | 2023-09-04 | 한국화학연구원 | Circulating fluidized bed reactor using electric heating furnace |
| IT202100023708A1 (en) * | 2021-09-14 | 2023-03-14 | Idrogena S R L | PLANT AND PROCEDURE FOR THE PRODUCTION OF HYDROGEN FROM SCISION OF METHANE MOLECULES |
| US11697099B2 (en) | 2021-11-22 | 2023-07-11 | Schneider Electric Systems Usa, Inc. | Direct electrical heating of catalytic reactive system |
| WO2024074277A1 (en) | 2022-10-07 | 2024-04-11 | Evonik Operations Gmbh | Catalytically active heating elements, production and use thereof |
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| EP0913357A1 (en) * | 1997-10-28 | 1999-05-06 | Ngk Insulators, Ltd. | Reformer and method for operation thereof |
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| US5477676A (en) * | 1988-04-15 | 1995-12-26 | Midwest Research Institute | Method and apparatus for thermal management of vehicle exhaust systems |
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| JP3891131B2 (en) * | 2002-03-29 | 2007-03-14 | カシオ計算機株式会社 | Chemical reaction apparatus and power supply system |
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2004
- 2004-04-02 WO PCT/EP2004/003529 patent/WO2004091773A1/en active Application Filing
- 2004-04-02 CN CNB2004800100288A patent/CN100381200C/en not_active Expired - Fee Related
- 2004-04-02 AU AU2004229151A patent/AU2004229151A1/en not_active Abandoned
-
2005
- 2005-10-13 ZA ZA200508311A patent/ZA200508311B/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0913357A1 (en) * | 1997-10-28 | 1999-05-06 | Ngk Insulators, Ltd. | Reformer and method for operation thereof |
| EP1085177A2 (en) * | 1999-09-20 | 2001-03-21 | Toyota Jidosha Kabushiki Kaisha | Regenerative catalytic apparatus in hybrid vehicle |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1774291A (en) | 2006-05-17 |
| DE10317197A1 (en) | 2004-11-04 |
| ZA200508311B (en) | 2007-03-28 |
| AU2004229151A1 (en) | 2004-10-28 |
| WO2004091773A1 (en) | 2004-10-28 |
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