CN104176703A - Catalytic membrane reactor, catalytic-coupling and separating membrane tube and manufacturing method of catalytic-coupling and separating membrane tube - Google Patents
Catalytic membrane reactor, catalytic-coupling and separating membrane tube and manufacturing method of catalytic-coupling and separating membrane tube Download PDFInfo
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- CN104176703A CN104176703A CN201410312350.1A CN201410312350A CN104176703A CN 104176703 A CN104176703 A CN 104176703A CN 201410312350 A CN201410312350 A CN 201410312350A CN 104176703 A CN104176703 A CN 104176703A
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- separation membrane
- coupled separation
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- membrane pipe
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to the technical field of catalytic hydrogen production and discloses a catalytic membrane reactor, a catalytic-coupling and separating membrane tube and a manufacturing method of the catalytic-coupling and separating membrane tube. The catalytic membrane reactor comprises a raw material storage tank for storing hydrogen iodide, a reaction tube connected with an outlet of the raw material storage tank, at least one catalytic-coupling and separating membrane tube which is sleeved by the reaction tube, a heater for heating the reaction tube and a first condensing purifier connected with an outlet of the reaction tube, wherein each catalytic-coupling and separating membrane tube comprises a silicon dioxide membrane on which active metals are loaded or a carbon membrane on which active metals are loaded. By adopting the technical scheme disclosed by the invention, the decomposition rate of the hydrogen iodide is increased.
Description
Technical field
The present invention relates to catalyzing manufacturing of hydrogen technical field, particularly relate to a kind of membrane catalytic reactor, a kind of catalysis coupled separation membrane pipe and preparation method thereof.
Background technology
Large-scale low-cost hydrogen manufacturing is the basis of development hydrogen economy, and traditional hydrogen production process is all taking fossil oil as raw material, along with the minimizing of fossil oil, and people then seek using water as hydrogen feedstock.Water decomposition hydrogen manufacturing is divided into the several methods such as electric decomposition, thermolysis and photolysis.The electric disaggregated cost of water is too high, photolysis from practical distance still away from, therefore the thermolysis of water attracts wide attention.The direct heat of water is decomposed the high temperature that at least needs 2773K, and under such high temperature, device materials all cannot normally be worked with the mould material that separates hydrogen and oxygen.Can under relatively mild condition, realize the efficient decomposition of water by a series of chemical reaction? thermochemical cycle water decomposition hydrogen production process is just based on above imagination, the chemical reaction that adopts series reaction thing can be recycled, finally realize the decomposition of water, energy utilization efficiency is expected to reach more than 50%.
The research of thermochemical cycle for hydrogen production method starts starting from the sixties in last century, and its maximum feature is that high, the required heat energy temperature of energy conversion efficiency is lower, reactive material recycle, can realize large-scale continuous hydrogen production.2002, (the General Atomics of AM General atom technology company, be called for short GA), Sandia National Laboratory of the U.S. and University of Kentucky combine 115 kinds of thermochemical cycle screened, in numerous circulations, thermochemistry sulphur iodine circulation (Sulfur – Iodine Thermochemical Cycle, be called for short SI or IS) high due to its reactions steps simplifications, reaction conditions gentleness, cycle efficiency, finally select the ideal cycle of this circulation as hydrogen manufacturing.In recent years paid much attention in the U.S., Japan and Korea S and Europe, become new academic frontier and the hot issue of current this area in the world research, various countries drop into one after another a large amount of human and material resources and competitively carry out correlative study.Therefore, the fundamental research of carrying out thermochemistry sulphur iodine circulation hydrogen manufacturing not only has very great scientific meaning, and have widely, the application prospect of reality.
Thermochemistry sulphur iodine circulation hydrogen manufacturing is made up of following three chemical reactions:
I
2+SO
2+2H
2O→2HI+H
2SO
4(20～120℃) (1)
2HI→I
2+H
2(300～500℃) (2)
H
2SO
4→SO
2+H
2O+0.5O
2(800～850℃) (3)
Wherein, the decomposition that reaction (2) is hydrogen iodide, at 300-500 DEG C of temperature, hydrogen iodide decomposes generation H
2and I
2, this is the committed step that the circulation of thermochemistry sulphur iodine produces hydrogen.Consider ability to bear and the energy consumption problem of equipment and materials, the temperature of hydrogen iodide decomposing gas should be too not high, but under middle low temperature, the speed of homogeneous chemical reaction is limited, therefore, generally accelerates the speed of hydrogen iodide decomposing gas with catalyzer.But the thermodynamic(al)equilibrium rate of decomposition of hydrogen iodide in the time of 500 DEG C is only 22% left and right, and this has caused a large amount of Matter Transfers and energy expenditure.
Existing solution is that the silicon dioxide film of surface sediment activated-carbon catalyst is applied to hydrogen iodide catalytic decomposition.As shown in Figure 1, Fig. 1 is the structural representation of the existing membrane catalytic reactor for hydrogen iodide catalytic decomposition, comprise hydrogen iodide gas tank 21, the reactor 22 being connected with hydrogen iodide gas tank 21, in reactor 22, be provided with silicon dioxide film 23, the upper surface of this silicon dioxide film 23 is piled up activated-carbon catalyst, the hydrogen that catalytic decomposition produces can be to the below infiltration of silicon dioxide film 23, below the inside of reactor 22 silicon dioxide film 23, adopt nitrogen as sweep gas, the product having reacted and nitrogen enter gas separator 24 and carry out gas delivery.In this membrane catalytic reactor, at the surface sediment activated-carbon catalyst of silicon dioxide film 23, can cause similar carbon distribution effect, this is unfavorable for the hydrogen permeate on silicon dioxide film 23 surfaces, in addition, the catalyzer of piling up can increase the resistance in reactor 22, piles up activated-carbon catalyst and also has catalyst loading and the problem such as fixing, makes the device of reactor 22 complicated.
The defect of prior art is, silicon dioxide film surface sediment activated-carbon catalyst can cause carbon distribution effect, causes hydrogen permeate Efficiency Decreasing, can not remove in time reaction product hydrogen, therefore makes hydrogen iodide rate of decomposition lower.
Summary of the invention
The object of this invention is to provide a kind of membrane reactor, a kind of catalysis coupled separation membrane pipe and preparation method thereof, in order to improve the rate of decomposition of hydrogen iodide cartalytic decomposition effect.
The embodiment of the present invention provides a kind of membrane catalytic reactor, and described membrane catalytic reactor, for the reaction of hydrogen iodide decomposing hydrogen-production, comprising:
Store the raw material storage tank of hydrogen iodide;
The reaction tubes being connected with the outlet of described raw material storage tank;
Be sheathed at least one catalysis coupled separation membrane pipe in described reaction tubes, every described catalysis coupled separation membrane pipe comprises the silicon dioxide film of supported active metal or the carbon film of supported active metal;
The well heater that described reaction tubes is heated; And
The first condensation purifier being connected with the outlet of described reaction tubes.
In technical solution of the present invention, adopt catalysis coupled separation membrane pipe, catalysis coupled separation membrane pipe has adopted the silicon dioxide film of supported active metal or the carbon film of supported active metal, with respect to the silicon dioxide film of existing accumulation gac, the carbon film of the silicon dioxide film of supported active metal or supported active metal is because its surface does not exist the gac of accumulation, can there is not the generation that is similar to carbon distribution effect, therefore hydrogen can keep good infiltration rate finally to enter condensation reactor at film tube-surface always, reduce the resistance in reaction tubes, reaction product hydrogen can remove in time, therefore improved the rate of decomposition of hydrogen iodide, also because hydrogen can remove in time, within the identical time, can there is more hydrogen iodide to decompose, improve the rate of decomposition of hydrogen iodide, and, owing to not adopting sweep gas, therefore, in reaction product, only there are hydrogen, a small amount of water, iodine and hydrogen iodide, reaction product can directly enter condensation reactor carries out condensation separation and obtains pure hydrogen, and does not need further to carry out gas delivery, has greatly shortened the time of hydrogen purification.In addition, on silicon dioxide film or carbon film, the active metal of load had both been conducive to improve the infiltration rate of hydrogen, can be used as again the catalytic active component of hydrogen iodide decomposing hydrogen-production reaction, improved the efficiency of hydrogen iodide decomposing hydrogen-production reaction.In addition, the silicon dioxide film of existing accumulation gac, also need certain strut member, prevent that the gac of piling up is scattered, but in the present invention, the load of the carbon film of the silicon dioxide film of supported active metal or supported active metal is chemical bond, do not need to arrange strut member, therefore, simplified the composition of membrane catalytic reactor.
Preferably, contriver finds, when the active metal in the silicon dioxide film of described supported active metal or the carbon film of supported active metal comprises one or more in palladium, niobium, tantalum and platinum, the load content of active metal is lower than 20% time, silicon dioxide film or carbon film have good hydrogen permeate efficiency, the promoter action that has again good catalysis hydrogen iodide to decompose.
Preferably, the mean pore size of described catalysis coupled separation membrane pipe is 0.03～0.1nm; The hydrogen permeate speed of described catalysis coupled separation membrane pipe is 1 × 10
-8molm
-2s
-1pa
-1～1 × 10
-5molm
-2s
-1pa
-1; The H of described catalysis coupled separation membrane pipe
2the selectivity of/HI is higher than 100.
For above-mentioned any membrane catalytic reactor, an end opening of every described catalysis coupled separation membrane pipe, the other end sealing.
The design that catalysis coupled separation membrane pipe adopts one end to seal an end opening, hydrogen iodide is in the outside surface generation decomposition reaction of catalysis coupled separation membrane pipe, and the hydrogen forming after decomposing enters catalysis coupled separation membrane pipe inside, flows out from opening one end.
Preferably, described membrane catalytic reactor, also comprises: the second condensation purifier being connected with described catalysis coupled separation membrane tube opening.
Hydrogen, mainly in the inside of catalysis coupled separation membrane pipe, therefore, can design the second condensation purifier hydrogen is carried out to condensation cleaning.
Preferably, described membrane catalytic reactor, also comprises:
Water storage tank;
With the vapour generator that described water storage tank is connected, the steam outlet pipeline of described vapour generator passes into the other end of every described catalysis coupled separation membrane pipe;
The first transferpump on pipeline between described water storage tank and described vapour generator.
Pass into water vapour as sweep gas in catalysis coupled separation membrane pipe inside, can improve hydrogen and remove speed in reaction tubes, increase hydrogen and be penetrated into the speed of catalysis coupled separation membrane pipe inside from catalysis coupled separation membrane tube outer surface, and then improved the rate of decomposition of hydrogen iodide.In addition, because the mixture of water vapour and hydrogen can obtain hydrogen by simple condensation cleaning, therefore adopt water vapour as sweep gas, can increase in addition separating device.
Preferably, described membrane catalytic reactor, also comprises:
Preheater on pipeline between described raw material storage tank and described reaction tubes.
Because hydrogen iodide decomposing hydrogen-production need to be heated to comparatively high temps, if only adopt the well heater that reaction tubes is heated, temperature in possible reaction tubes is lower than the temperature of reaction needed, therefore, before hydrogen iodide enters reaction tubes, first preheat, prevent real reaction temperature in the reaction tubes problem lower than desired reaction temperature.
Preferably, described membrane catalytic reactor, also comprises:
The second transferpump on pipeline between described raw material storage tank and described preheater.
The second transferpump is for delivery of hydrogen iodide gas or hydrogen iodide solution (claiming again hydroiodic acid HI).
The material of reaction tubes can have multiple choices, as long as do not react with hydrogen iodide and degradation production thereof under temperature of reaction, preferred, the material of described reaction tubes comprises quartz or stainless steel.
Preferably, the supporter of described catalysis coupled separation membrane pipe comprises porous ceramic pipe, and described catalysis coupled separation membrane pipe is straight tube or coil pipe.For example, porous ceramic pipe is alumina porous ceramic pipe.
Based on identical inventive concept, the embodiment of the present invention also provides a kind of making method of catalysis coupled separation membrane pipe, comprising:
Using porous ceramic pipe as supporter, form silicon dioxide film or carbon film in described supporting body surface;
Adopt metal salt solution pickling process supported active metal on described silicon dioxide film or carbon film, form described catalysis coupled separation membrane pipe, wherein, described catalysis coupled separation membrane pipe is the catalysis coupled separation membrane pipe in aforesaid membrane catalytic reactor.
In above-mentioned making method, porous ceramic pipe can adopt alumina porous ceramic pipe; Form silicon dioxide film in supporting body surface, can be with tetraethoxy as presoma, roasting preparation under 650 DEG C of temperature condition; Form carbon film in supporting body surface, can adopt glycan alcohol is presoma, roasting preparation under 700 DEG C of temperature condition.
The embodiment of the present invention also provides a kind of catalysis coupled separation membrane pipe, and described catalysis coupled separation membrane pipe adopts the making method of above-mentioned catalysis coupled separation membrane pipe to obtain.
Brief description of the drawings
Fig. 1 is the structural representation of the existing membrane catalytic reactor for hydrogen iodide catalytic decomposition;
The structural representation of the membrane catalytic reactor that Fig. 2 provides for first embodiment of the invention;
The structural representation of the membrane catalytic reactor that Fig. 3 provides for second embodiment of the invention;
The structural representation of the membrane catalytic reactor that Fig. 4 provides for third embodiment of the invention.
Reference numeral:
1-raw material storage tank 2-the second transferpump 3-preheater 4-reaction tubes 5-well heater
6-the second condensation purifier 7-catalysis coupled separation membrane pipe 8-vapour generator
9-first transferpump 10-water storage tank 11-the first condensation purifier
12-switch-valve 21-hydrogen iodide gas tank 22-reactor
23-silicon dioxide film 24-gas separator
Embodiment
In order to improve the speed of hydrogen iodide cartalytic decomposition effect, the invention provides a kind of membrane catalytic reactor for hydrogen iodide decomposing hydrogen-production, a kind of catalysis coupled separation membrane pipe and preparation method thereof.In this technical scheme, adopt catalysis coupled separation membrane pipe, catalysis coupled separation membrane pipe has adopted the silicon dioxide film of supported active metal or the carbon film of supported active metal, with respect to the silicon dioxide film of existing accumulation gac, the carbon film of the silicon dioxide film of supported active metal or supported active metal is because its surface does not exist the gac of accumulation, can there is not the generation that is similar to carbon distribution effect, therefore hydrogen can keep good infiltration rate finally to enter condensation reactor at film tube-surface always, reduce the resistance in reaction tubes, reaction product hydrogen can remove in time, therefore improved the rate of decomposition of hydrogen iodide.For making the object, technical solutions and advantages of the present invention clearer, below lift specific embodiment the present invention is described in further detail.
The embodiment of the present invention provides a kind of membrane catalytic reactor, as shown in Figure 2, the structural representation of the membrane catalytic reactor that Fig. 2 provides for first embodiment of the invention, described membrane catalytic reactor, for the reaction of hydrogen iodide decomposing hydrogen-production, comprising:
Store the raw material storage tank 1 of hydrogen iodide;
The reaction tubes 4 being connected with the outlet of raw material storage tank 1;
Be sheathed at least one catalysis coupled separation membrane pipe 7 in reaction tubes 4, every catalysis coupled separation membrane pipe 7 comprises the silicon dioxide film of supported active metal or the carbon film of supported active metal;
The well heater 5 that reaction tubes 4 is heated; And
The first condensation purifier 11 being connected with the outlet of reaction tubes 4.
In technical solution of the present invention, adopt catalysis coupled separation membrane pipe 7, catalysis coupled separation membrane pipe 7 has adopted the silicon dioxide film of supported active metal or the carbon film of supported active metal, with respect to the silicon dioxide film of existing accumulation gac, the carbon film of the silicon dioxide film of supported active metal or supported active metal is because its surface does not exist the gac of accumulation, can there is not the generation that is similar to carbon distribution effect, therefore hydrogen can keep good infiltration rate finally to enter condensation reactor at film tube-surface always, reduce the resistance in reaction tubes 4, reaction product hydrogen can remove in time, within the identical time, can there is more hydrogen iodide to decompose, therefore improved the rate of decomposition of hydrogen iodide, and, owing to not adopting sweep gas, therefore, in reaction product, only there are hydrogen, a small amount of water and hydrogen iodide, reaction product can directly enter the first condensation purifier 11 carries out condensation separation and obtains pure hydrogen, and does not need further to carry out gas delivery, has greatly shortened the time of hydrogen purification.In addition, on silicon dioxide film or carbon film, the active metal of load had both been conducive to improve the infiltration rate of hydrogen, can be used as again the catalytic active component of hydrogen iodide decomposing hydrogen-production reaction, improved the efficiency of hydrogen iodide decomposing hydrogen-production reaction.In addition, the silicon dioxide film of existing accumulation gac, also need certain strut member, prevent that the gac of piling up is scattered, but in the present invention, the load of the carbon film of the silicon dioxide film of supported active metal or supported active metal is chemical bond, do not need to arrange strut member, therefore, simplified the composition of membrane catalytic reactor.
Shown in Fig. 2, in technical solution of the present invention, raw material storage tank 1 is for raw material storage, wherein stored raw material can be hydrogen iodide gas or hydrogen iodide solution (claiming again hydroiodic acid HI solution), this raw material can inject raw material storage tank 1 by manual/auto mode, and the present invention is not construed as limiting this.In technical solution of the present invention, do not limit the structure of catalysis coupled separation membrane pipe 7, catalysis coupled separation membrane pipe 7 comprises the carbon film of the supporter of porous and the silicon dioxide film of supported active metal or supported active metal, the carbon film of the silicon dioxide film of described supported active metal or supported active metal can be positioned at the hole of supporter, and outside surface and/or internal surface, catalysis coupled separation membrane pipe 7 can an end opening, the other end sealing, also can all openings of two ends, preferably adopt the structure of catalysis coupled separation membrane pipe 7 one end opening the other end sealings, in the time that the silicon dioxide film of supported active metal or the carbon film of supported active metal are positioned at the outside surface of catalysis coupled separation membrane pipe 7, hydrogen iodide is in the outside surface generation decomposition reaction of catalysis coupled separation membrane pipe 7, hydrogen permeate enters the inside of catalysis coupled separation membrane pipe 7, in the time that the silicon dioxide film of supported active metal or the carbon film of supported active metal are positioned at the internal surface of catalysis coupled separation membrane pipe 7, hydrogen iodide is in the internal surface generation decomposition reaction of catalysis coupled separation membrane pipe 7, and hydrogen permeate is to the outside of catalysis coupled separation membrane pipe 7.The structure of the catalysis coupled separation membrane pipe in following embodiment 1～7 is the silicon dioxide film of supported active metal or the carbon film of supported active metal and is positioned at the outside surface of catalysis coupled separation membrane pipe.The quantity of catalysis coupled separation membrane pipe 7 can be one, two, three, five, ten, even more, and preferably one to ten.
Preferably, contriver finds, when the active metal in the silicon dioxide film of described supported active metal or the carbon film of supported active metal comprises one or more in palladium (Pd), niobium (Nb), tantalum (Ta) and platinum (Pt), the load content of active metal is lower than 20% time, silicon dioxide film or carbon film have good hydrogen permeate efficiency, the promoter action that has again good catalysis hydrogen iodide to decompose.
Preferably, the mean pore size of described catalysis coupled separation membrane pipe is 0.03～0.1nm; The hydrogen permeate speed of described catalysis coupled separation membrane pipe is 1 × 10
-8molm
-2s
-1pa
-1～1 × 10
-5molm
-2s
-1pa
-1; The H of described catalysis coupled separation membrane pipe
2the selectivity of/HI is higher than 100.
The H of described catalysis coupled separation membrane pipe
2/ H
2o selectivity exceedes 3.
The silicon dioxide film of above-mentioned supported active metal adopts silicon dioxide film as carrier, silicon dioxide film is taking alumina porous ceramic as matrix, can adopt silicon dioxide gel or chemical vapour deposition (CVD) method, in the time of 650 DEG C of temperature, deposit roasting preparation, the carrying method of active metal can adopt metal salt solution pickling process to carry out load, and the present invention does not limit this making method.
The carbon film of above-mentioned supported active metal adopts carbon film as carrier, carbon film is taking alumina porous ceramic as matrix, can adopt glycan alcohol is presoma, when 700 DEG C of temperature, in argon gas atmosphere, prepare, the carrying method of active metal can adopt metal salt solution pickling process to carry out load, and the present invention states making method and do not limit this.
Shown in Fig. 2, for above-mentioned any membrane catalytic reactor, an end opening of every catalysis coupled separation membrane pipe 7, the other end sealing.
Catalysis coupled separation membrane pipe 7 adopts one end to seal the design of an end opening, and hydrogen iodide is in the outside surface generation decomposition reaction of catalysis coupled separation membrane pipe 7, and the hydrogen forming after decomposing enters the inside of catalysis coupled separation membrane pipe 7, flows out from opening one end.
Shown in Fig. 2, preferred, described membrane catalytic reactor, also comprises: the second condensation purifier 6 being connected with catalysis coupled separation membrane pipe 7 openings.
Hydrogen, mainly in the inside of catalysis coupled separation membrane pipe 7, therefore, can design the second condensation purifier 6 hydrogen is carried out to condensation cleaning.Product after the first above-mentioned condensation purifier 11 and the second condensation purifier 6 decompose for HI purifies, and temperature can be-20～20 DEG C, and degradation production is HI, I
2, H
2o and H
2mixed gas, after the first condensation purifier 11 and the second condensation purifier 6 condensation cleanings, obtains pure H
2.
As shown in Figure 3, the structural representation of the membrane catalytic reactor that Fig. 3 second embodiment of the invention provides, preferred, described membrane catalytic reactor, also comprises:
Water storage tank 10;
The vapour generator 8 being connected with water storage tank 10, the steam outlet pipeline of vapour generator 8 passes into the other end of every catalysis coupled separation membrane pipe 7;
The first transferpump 9 on pipeline between water storage tank 10 and vapour generator 8.
Pass into water vapour as sweep gas in catalysis coupled separation membrane pipe 7 inside, can improve hydrogen and remove speed in reaction tubes, increase hydrogen and be penetrated into the speed of catalysis coupled separation membrane pipe 7 inside from catalysis coupled separation membrane pipe 7 outside surfaces, and then improved the rate of decomposition of hydrogen iodide.In addition, because the mixture of water vapour and hydrogen can obtain hydrogen by simple condensation cleaning, therefore adopt water vapour as sweep gas, can increase in addition separating device.
Shown in Fig. 2 or Fig. 3, preferred, described membrane catalytic reactor, also comprises:
Preheater 3 on pipeline between raw material storage tank 1 and reaction tubes 4.
Because hydrogen iodide decomposing hydrogen-production need to be heated to comparatively high temps, if only adopt the well heater that reaction tubes 4 is heated, temperature in possible reaction tubes 4 is lower than the temperature of reaction needed, therefore, before hydrogen iodide enters reaction tubes 4, first preheat, prevent real reaction temperature in the reaction tubes problem lower than desired reaction temperature.The material of preheater 3 can be the stainless steel of tetrafluoroethylene, quartz or liner tantalum, and the temperature of preheating can be set to 110～200 DEG C, and the structure of preheater 3 can adopt the mode of heating zone, tube furnace or interchanger.
In addition, in order to make the structure-integrated of membrane separation reactor, can also comprise the switch-valve 12 between preheater 3 and water storage tank 10.
Shown in Fig. 2 or Fig. 3, preferred, described membrane catalytic reactor, also comprises:
The second transferpump 2 on pipeline between raw material storage tank 1 and preheater 3.
The second transferpump 2 is for delivery of hydrogen iodide gas or hydroiodic acid HI.The type of the first transferpump 9 and the second transferpump 2 is not limit, and can be corrosion resistant peristaltic pump, surge pump, mechanical pump or off-gas pump.
Shown in Fig. 2 or Fig. 3, the material of reaction tubes 4 can have multiple choices, as long as do not react with hydrogen iodide and degradation production thereof under temperature of reaction, preferred, the material of described reaction tubes 4 comprises quartz or stainless steel.The temperature of reaction tubes 4 can be 300～600 DEG C, can adopt the mode of tube furnace or interchanger to heat reaction tubes 4.
Shown in Fig. 2 or Fig. 3, preferred, the supporter of catalysis coupled separation membrane pipe 7 comprises porous ceramic pipe, and described catalysis coupled separation membrane pipe 7 is straight tube or coil pipe.For example, porous ceramic pipe is alumina porous ceramic pipe.Catalysis coupled separation membrane pipe 7 can be single passage, can be also hyperchannel form.
As shown in Figure 4, the structural representation of the membrane catalytic reactor that Fig. 4 provides for third embodiment of the invention wherein has at least two catalysis coupled separation membrane pipes 7, catalysis coupled separation membrane pipe more than 7 in reaction tubes 4, heat-transfer effect can be better, and the rate of decomposition of hydrogen iodide is improved.
Based on identical inventive concept, the embodiment of the present invention also provides a kind of making method of catalysis coupled separation membrane pipe, comprising:
Using porous ceramic pipe as supporter, form silicon dioxide film or carbon film in described supporting body surface;
Adopt metal salt solution pickling process supported active metal on described silicon dioxide film or carbon film, form described catalysis coupled separation membrane pipe, wherein, described catalysis coupled separation membrane pipe is the catalysis coupled separation membrane pipe in aforesaid membrane catalytic reactor.
In above-mentioned making method, porous ceramic pipe can adopt alumina porous ceramic pipe; Form silicon dioxide film in supporting body surface, can be with tetraethoxy as presoma, roasting preparation under 650 DEG C of temperature condition, concrete method can adopt silicon dioxide gel or chemical gaseous phase depositing process; Form carbon film in supporting body surface, can adopt glycan alcohol is presoma, roasting preparation under 700 DEG C of temperature condition.
The embodiment of the present invention also provides a kind of catalysis coupled separation membrane pipe, and described catalysis coupled separation membrane pipe adopts the making method of above-mentioned catalysis coupled separation membrane pipe to obtain.Catalysis coupled separation membrane pipe has adopted the silicon dioxide film of supported active metal or the carbon film of supported active metal, adopt this catalysis coupled separation membrane pipe as the catalytic separation device in hydrogen iodide decomposition reaction membrane reactor used, active metal can be for catalytic iodine H-H reaction, and whole film pipe also has centrifugation, can make the hydrogen generating keep good infiltration rate at film tube-surface always, and then can remove as early as possible hydrogen, improve the rate of decomposition of hydrogen iodide.
Below enumerate preferred embodiment and illustrate that membrane catalytic reactor of the present invention is for hydrogen iodide decomposing hydrogen-production, but the present invention is not limited to following examples.
The catalysis coupled separation membrane pipe that the embodiment of the present invention adopts can make by the following method, but invention is not limited to following method:
One, the making method of the silicon dioxide film pipe of supported active metal: adopt the supporter of alumina ceramic tube as silicon dioxide film.Presoma is tetraethoxy (TEOS) and is placed in storage tank, maintains 30 DEG C of constant temperature, through N
2carry and enter generating tube (160 DEG C) and carry out preheating, enter subsequently load area and γ-Al
2o
3the contact of modification porous ceramic pipe, when temperature is 650 DEG C, TEOS pyrolysis generates SiO
2.Vacuum drawn film pipe inner side, the SiO of generation
2load on supporter outside surface, vacuumometer is measured vacuum tightness in film pipe.Along with SiO
2load, supporting body surface aperture progressively dwindles, and in the time that film pipe inner side reaches certain vacuum and spends, must test required silicon dioxide film;
By above-mentioned silicon dioxide film precursor solution dipping 2h at active metal at 60 DEG C, then take out the dry 12h of silicon fiml, subsequently under argon gas (Ar) atmosphere, be warming up to 700 DEG C and constant temperature 3h with the temperature rise rate of 60 DEG C/h, then with the cold silicon dioxide film that obtains supported active metal of stove.
Two, the making method of the carbon film pipe of supported active metal: adopt the supporter of alumina ceramic tube as carbon film.Sugar alcohol is through Catalyzed by Oxalic Acid effect, and at 70 DEG C of temperature, 12h stirs, and the glycan alcohol obtaining is as carbon film presoma.After being immersed to glycan alcoholic solution 5min, takes out ceramic supporting body dry 12h at 80 DEG C of temperature.Sample, under Ar atmosphere, is warming up to 700 DEG C and constant temperature 4h with the temperature rise rate of 60 DEG C/h, then cold with stove.Through above-mentioned coating procedure repeatedly, obtain required carbon film;
By above-mentioned carbon film precursor solution dipping 2h at active metal at 60 DEG C, then take out the dry 12h of carbon film, under Ar atmosphere, be warming up to 700 DEG C and constant temperature 3h with the temperature rise rate of 60 DEG C/h, then with the cold carbon film that obtains supported active metal of stove subsequently.
Embodiment 1
In the membrane catalytic reactor shown in Fig. 3, carry out the reaction of hydrogen iodide decomposing hydrogen-production, the quantity of catalysis coupled separation membrane pipe 7 is one, these catalysis coupled separation membrane pipe 7 one end openings, one end sealing.In raw material storage tank 1, store hydrogen iodide gas, hydrogen iodide gas is by the second transferpump 2 (selecting corrosion-resistant off-gas pump) charging, hydrogen iodide flow 100ml/min, preheater 3 temperature are made as 160 DEG C, the temperature of well heater 5 is made as 600 DEG C, and the temperature of reaction tubes 4 is 600 DEG C, and catalysis coupled separation membrane pipe 7 adopts the silicon dioxide film of supporting Pt on porous ceramics (platinum), Pt load content is 10%, and penetrating quality is 5 × 10
-7mol s
-1m
-2pa
-1, H
2/ HI selectivity is 300, membrane area 4 × 10
-1m
2steam rates 30g/min, the degradation production of the inside of catalysis coupled separation membrane pipe 7 is through the second condensation purifier 6 condensations, purification and collection, and the outside cleavage reaction product of catalysis coupled separation membrane pipe 7, through the first condensation purifier 11 condensations, purification and collection, obtains pure hydrogen.After testing, hydrogen iodide rate of decomposition reaches 65%.
Embodiment 2
In the membrane catalytic reactor shown in Fig. 3, carry out the reaction of hydrogen iodide decomposing hydrogen-production, the quantity of catalysis coupled separation membrane pipe 7 is one, these catalysis coupled separation membrane pipe 7 one end openings, one end sealing.In raw material storage tank 1, store hydrogen iodide solution, hydrogen iodide solution (55.5wt.%) is by the second transferpump 2 (selecting corrosion-resistant peristaltic pump) charging, hydrogen iodide solution flow 200ml/min, preheater 3 temperature are made as 160 DEG C, the temperature of well heater 5 is made as 600 DEG C, and the temperature of reaction tubes 4 is 600 DEG C, and catalysis coupled separation membrane pipe 7 adopts the carbon film of supporting Pt on porous ceramics, Pt load content is 5%, and penetrating quality is 8 × 10
-7mol s
-1m
-2pa
-1, H
2/ HI selectivity is 150, membrane area 4 × 10
-1m
2steam rates 15g/min, the degradation production of the inside of catalysis coupled separation membrane pipe 7 is through the second condensation purifier 6 condensations, purification and collection, the outside cleavage reaction product of catalysis coupled separation membrane pipe 7 through condensation, purification and collection, obtains pure hydrogen through the first condensation purifier 11.After testing, hydrogen iodide rate of decomposition reaches 26%.
Embodiment 3
In the membrane catalytic reactor shown in Fig. 4, carry out the reaction of hydrogen iodide decomposing hydrogen-production, the quantity of catalysis coupled separation membrane pipe 7 is three, these catalysis coupled separation membrane pipe 7 one end openings, one end sealing.In raw material storage tank 1, store hydrogen iodide gas, hydrogen iodide gas is by the second transferpump 2 (selecting corrosion-resistant off-gas pump) charging, hydrogen iodide flow 50ml/min, preheating tube 3 temperature are made as 160 DEG C, the temperature of well heater 5 is made as 600 DEG C, and the temperature of reaction tubes 4 is 600 DEG C, and three catalysis coupled separation membrane pipes 7 all adopt the silicon dioxide film of supporting Pt on porous ceramics, Pt load content is 3%, and penetrating quality is 5 × 10
-7mol s
-1m
-2pa
-1, H
2/ HI selectivity is 300, membrane area 2 × 10
-1m
2the degradation production of the inside of catalysis coupled separation membrane pipe 7 is through the second condensation purifier 6 condensations, purification and collection, the outside cleavage reaction product of catalysis coupled separation membrane pipe 7, through the first condensation purifier 11 condensations, purification and collection, obtains pure hydrogen.After testing, hydrogen iodide rate of decomposition reaches 32%.
Embodiment 4
In the membrane catalytic reactor shown in Fig. 3, carry out the reaction of hydrogen iodide decomposing hydrogen-production, the quantity of catalysis coupled separation membrane pipe 7 is one, these catalysis coupled separation membrane pipe 7 one end openings, one end sealing.In raw material storage tank 1, store hydrogen iodide gas, hydrogen iodide gas is by the second transferpump 2 (selecting corrosion resisting diaphragm pump) charging, hydrogen iodide flow 60ml/min, preheating tube 3 temperature are made as 160 DEG C, the temperature of well heater 5 is made as 600 DEG C, and the temperature of reaction tubes 4 is 600 DEG C, and catalysis coupled separation membrane pipe 7 adopts the silicon dioxide film of load P d (palladium) on porous ceramics, Pd load content is 10%, and penetrating quality is 4 × 10
-7mol s
-1m
-2pa
-1, H
2/ HI selectivity is 300, membrane area 2 × 10
-1m
2steam rates 15g/min, the degradation production of the inside of catalysis coupled separation membrane pipe 7 is through the second condensation purifier 6 condensations, purification and collection, and the outside cleavage reaction product of catalysis coupled separation membrane pipe 7, through the first condensation purifier 11 condensations, purification and collection, obtains pure hydrogen.After testing, hydrogen iodide rate of decomposition reaches 40%.
Embodiment 5
Carry out the reaction of hydrogen iodide decomposing hydrogen-production removing in the membrane catalytic reactor shown in Fig. 3 of preheater 3, the quantity of catalysis coupled separation membrane pipe 7 is one, these catalysis coupled separation membrane pipe 7 one end openings, one end sealing.In raw material storage tank 1, store hydrogen iodide gas, hydrogen iodide gas is by the second transferpump 2 (selecting corrosion-resistant off-gas pump) charging, hydrogen iodide flow 100ml/min, the temperature of well heater 5 is made as 600 DEG C, catalysis coupled separation membrane pipe 7 adopts the silicon dioxide film of supporting Pt on porous ceramics, Pt load content is 10%, and penetrating quality is 5 × 10
-7mol s
-1m
-2pa
-1, H
2/ HI selectivity is 300, membrane area 4 × 10
-1m
2steam rates 30g/min, the degradation production of the inside of catalysis coupled separation membrane pipe 7 is through the second condensation purifier 6 condensations, purification and collection, and the outside cleavage reaction product of catalysis coupled separation membrane pipe 7, through the first condensation purifier 11 condensations, purification and collection, obtains pure hydrogen.After testing, hydrogen iodide rate of decomposition reaches 46%.
Embodiment 6
In the membrane catalytic reactor shown in Fig. 4, carry out the reaction of hydrogen iodide decomposing hydrogen-production, the quantity of catalysis coupled separation membrane pipe 7 is ten, these catalysis coupled separation membrane pipe 7 one end openings, one end sealing.In raw material storage tank 1, store hydrogen iodide gas, hydrogen iodide gas is by the second transferpump 2 (selecting corrosion-resistant off-gas pump) charging, hydrogen iodide flow 50ml/min, the temperature of preheating tube 3 is made as 160 DEG C, the temperature of well heater 5 is made as 600 DEG C, and the temperature of reaction tubes 4 is 600 DEG C, and ten catalysis coupled separation membrane pipes all adopt the silicon dioxide film of supporting Pt on porous ceramics, Pt load content is 10%, and penetrating quality is 5 × 10
-7mol s
-1m
-2pa
-1, H
2/ HI selectivity is 300, membrane area 2 × 10
-1m
2the degradation production of the inside of catalysis coupled separation membrane pipe 7 is through the second condensation purifier 6 condensations, purification and collection, the outside cleavage reaction product of catalysis coupled separation membrane pipe 7, through the first condensation purifier 11 condensations, purification and collection, obtains pure hydrogen.After testing, hydrogen iodide rate of decomposition reaches 78%.
Embodiment 7
In the membrane catalytic reactor shown in Fig. 3, carry out the reaction of hydrogen iodide decomposing hydrogen-production, the quantity of catalysis coupled separation membrane pipe 7 is one, these catalysis coupled separation membrane pipe 7 one end openings, one end sealing, just supported active metal not on catalysis coupled separation membrane pipe.In raw material storage tank 1, store hydrogen iodide gas, hydrogen iodide gas is by the second transferpump 2 (selecting corrosion-resistant off-gas pump) charging, hydrogen iodide flow 100ml/min, the temperature of preheating tube 3 is made as 160 DEG C, the temperature of well heater 5 is made as 600 DEG C, the temperature of reaction tubes 4 is 600 DEG C, and catalysis coupled separation membrane pipe adopts the carbon film that there is no any active metal of load on porous ceramics, and penetrating quality is 5 × 10
-7mol s
-1m
-2pa
-1, H
2/ HI selectivity is 300, membrane area 4 × 10
-1m
2steam rates 30g/min, the degradation production of the inside of catalysis coupled separation membrane pipe 7 is through the second condensation purifier 6 condensations, purification and collection, and the outside cleavage reaction product of catalysis coupled separation membrane pipe 7, through the first condensation purifier 11 condensations, purification and collection, obtains pure hydrogen.After testing, hydrogen iodide rate of decomposition reaches 17%.
In the above-described embodiments, hydrogen iodide rate of decomposition equals the ratio of the molar weight of twice purified hydrogen and the molar weight of the hydrogen iodide from raw material storage tank output.
From the test-results of above-described embodiment, with respect to existing membrane catalytic reactor, membrane catalytic reactor of the present invention can be broken the thermodynamic(al)equilibrium that hydrogen iodide decomposes, and greatly improves the rate of decomposition of hydrogen iodide, can reduce hydrogen iodide Matter Transfer number of times and energy wastage.The catalysis coupled separation membrane pipe adopting adopts silicon dioxide film or the carbon film of supported active metal on porous ceramics, the doping of active metal had both been conducive to improve the infiltration rate of gas separation membrane, the catalytic active component decomposing as HI again, this has just exempted from catalyst buildup on film surface, reduce the resistance in reactor, simplified membrane catalytic reaction apparatus.Adopt water vapor as sweep gas, can obtain purified hydrogen by simple condensation cleaning, reduced the cost of hydrogen purification.
Obviously, those skilled in the art can carry out various changes and modification and not depart from the spirit and scope of the present invention the present invention.Like this, if these amendments of the present invention and within modification belongs to the scope of the claims in the present invention and equivalent technologies thereof, the present invention is also intended to comprise these changes and modification interior.
Claims (10)
1. a membrane catalytic reactor, for the reaction of hydrogen iodide decomposing hydrogen-production, is characterized in that, comprising:
Store the raw material storage tank of hydrogen iodide;
The reaction tubes being connected with the outlet of described raw material storage tank;
Be sheathed at least one catalysis coupled separation membrane pipe in described reaction tubes, described catalysis coupled separation membrane pipe comprises the silicon dioxide film of supported active metal or the carbon film of supported active metal;
The well heater that described reaction tubes is heated; And
The first condensation purifier being connected with the outlet of described reaction tubes.
2. membrane catalytic reactor as claimed in claim 1, it is characterized in that, active metal in the carbon film of the silicon dioxide film of described supported active metal or supported active metal comprises one or more in palladium, niobium, tantalum and platinum, and the load content of active metal is lower than 20%.
3. membrane catalytic reactor as claimed in claim 2, is characterized in that, the mean pore size of described catalysis coupled separation membrane pipe is 0.03～0.1nm; The hydrogen permeate speed of described catalysis coupled separation membrane pipe is 1 × 10
-8molm
-2s
-1pa
-1～1 × 10
-5molm
-2s
-1pa
-1; The H of described catalysis coupled separation membrane pipe
2the selectivity of/HI is higher than 100.
4. the membrane catalytic reactor as described in claim 1～3 any one, is characterized in that, an end opening of every described catalysis coupled separation membrane pipe, the other end sealing.
5. membrane catalytic reactor as claimed in claim 4, is characterized in that, also comprises: the second condensation purifier being connected with described catalysis coupled separation membrane tube opening.
6. membrane catalytic reactor as claimed in claim 4, is characterized in that, also comprises:
Water storage tank;
With the vapour generator that described water storage tank is connected, the steam outlet pipeline of described vapour generator passes into the other end of every described catalysis coupled separation membrane pipe;
The first transferpump on pipeline between described water storage tank and described vapour generator.
7. membrane catalytic reactor as claimed in claim 1, is characterized in that, also comprises:
Preheater on pipeline between described raw material storage tank and described reaction tubes.
8. membrane catalytic reactor as claimed in claim 7, is characterized in that, also comprises:
The second transferpump on pipeline between described raw material storage tank and described preheater.
9. a making method for catalysis coupled separation membrane pipe, is characterized in that, comprising:
Using porous ceramic pipe as supporter, form silicon dioxide film or carbon film in described supporting body surface;
Adopt metal salt solution pickling process supported active metal on described silicon dioxide film or carbon film, form described catalysis coupled separation membrane pipe, wherein, described catalysis coupled separation membrane pipe is the catalysis coupled separation membrane pipe in membrane catalytic reactor as claimed in claim 1.
10. a catalysis coupled separation membrane pipe, is characterized in that, described catalysis coupled separation membrane pipe adopts the making method of catalysis coupled separation membrane pipe as claimed in claim 9 to obtain.
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Cited By (5)
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| CN108854928A (en) * | 2018-07-05 | 2018-11-23 | 山东理工大学 | Preparation method preparing hydrogen by ammonia decomposition reaction and separate economic benefits and social benefits ceramic of compact membrane reactor |
| CN109437100A (en) * | 2018-11-26 | 2019-03-08 | 清华大学 | A kind of hydroiodic acid decomposing hydrogen-production reactor and its hydrogen production process |
| CN110436410A (en) * | 2019-08-20 | 2019-11-12 | 中核能源科技有限公司 | A kind of high temperature gas cooled reactor coupling iodine selenium thermochemical cycles carbon reduction hydrogen production process |
| CN114939386A (en) * | 2022-06-02 | 2022-08-26 | 苏州道一至诚纳米材料技术有限公司 | Membrane catalytic reaction device |
| CN115010087A (en) * | 2022-08-08 | 2022-09-06 | 浙江百能科技有限公司 | HI decomposition hydrogen production membrane reactor and hydrogen production method and system thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108854928A (en) * | 2018-07-05 | 2018-11-23 | 山东理工大学 | Preparation method preparing hydrogen by ammonia decomposition reaction and separate economic benefits and social benefits ceramic of compact membrane reactor |
| CN109437100A (en) * | 2018-11-26 | 2019-03-08 | 清华大学 | A kind of hydroiodic acid decomposing hydrogen-production reactor and its hydrogen production process |
| CN109437100B (en) * | 2018-11-26 | 2023-09-05 | 清华大学 | Reactor for hydrogen production by hydroiodic acid decomposition and hydrogen production method thereof |
| CN110436410A (en) * | 2019-08-20 | 2019-11-12 | 中核能源科技有限公司 | A kind of high temperature gas cooled reactor coupling iodine selenium thermochemical cycles carbon reduction hydrogen production process |
| CN114939386A (en) * | 2022-06-02 | 2022-08-26 | 苏州道一至诚纳米材料技术有限公司 | Membrane catalytic reaction device |
| CN115010087A (en) * | 2022-08-08 | 2022-09-06 | 浙江百能科技有限公司 | HI decomposition hydrogen production membrane reactor and hydrogen production method and system thereof |
| CN115010087B (en) * | 2022-08-08 | 2022-11-11 | 浙江百能科技有限公司 | HI decomposition hydrogen production membrane reactor and hydrogen production method and system thereof |
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