CN106276794B - Hydrogen-manufacturing reactor - Google Patents
Hydrogen-manufacturing reactor Download PDFInfo
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- CN106276794B CN106276794B CN201610483078.2A CN201610483078A CN106276794B CN 106276794 B CN106276794 B CN 106276794B CN 201610483078 A CN201610483078 A CN 201610483078A CN 106276794 B CN106276794 B CN 106276794B
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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
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
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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
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
- H01M8/0668—Removal of carbon monoxide or carbon dioxide
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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
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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
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam 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
- C01B2203/02—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
- C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
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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
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition 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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift 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
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
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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
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
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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
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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
- C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
- C01B2203/84—Energy production
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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
- Y02E60/50—Fuel cells
Abstract
The present invention relates to a kind of reactors that hydrogeneous reformation gas is generated by the raw material comprising carbon compound and water, and the reactor includes: reforming section, generates hydrogeneous reformation gas by reforming the raw material；Combustion section supplies heat to above-mentioned reforming section by burning the raw material；Carbon monoxide removal reacting part removes the hydrogeneous carbon monoxide reformed in gas；Heat feed line；And reformer feed phase transition tube, in combustion section, and raw material is heated, wherein, successively it is separated by from outside with concentric structure and is provided with first shell, second shell and heating feed line, the reforming section and combustion section is individually formed by the first shell and being separated by space and the second shell and heating being separated by space of feed line of institute's second shell respectively.
Description
Technical field
The present invention relates to a kind of hydrogen-manufacturing reactor, which is converted into hydrogeneous weight by reforming carbon compound
Whole gas is simultaneously supplied in fuel cell.In particular it relates to a kind of hydrogen-manufacturing reactor by carbon compound production hydrogen, the hydrogen manufacturing is anti-
Answering device is the raw material of the phase transformation portion gasification of the liquid charging stock by evaporation mixing carbon compound and water in the weight for being filled with catalyst
Hydrogeneous reformation gas is converted into whole reacting part, in order to promote the reaction and with reforming reaction part from adjoining flow path on set
Combustion reaction portion is set, and inducing moiety liquid charging stock carries out combustion reaction on a catalyst, thus the heat that combustion reaction is generated
It is supplied in reforming reaction portion as reaction heat.
Background technique
In recent years, with the increase of the attention rate to environmental problem, to using hydrogen as the concern of the clean fuel of fuel and
Demand is also increasing.For high molecular fuel battery system as efficient power generator, the operating temperature of the system is low and can
Quick start, if therefore connect with hydrogen gas supplying apparatus appropriate, can be used as multipurpose power supply device.
Carbon compound comprising methanol is free of sulfur component and hydrogen with higher/carbon-ratio characteristic molecular structure, simultaneously
It is easy to mix with water, and is liquid under room temperature, normal pressure, therefore the carbon compound is the combustion for being easy to store with high-energy density
Material.As one of the method by the carbon compound production hydrogen including methanol, steam reforming method has been developed, and
The steam reforming method is widely used.
In order to carry out steam reforming reaction by carbon compound, it is necessary first to for making the carbon compound of liquid and mixing for water
Close the gasifier of object gasification, for the burner to reforming reactor supply heat and for making liquid fuels for combustion gasify
Gasifier, when supply is into the polymer fuel cell vulnerable to carbon monoxide image of such as polymer fuel cell, in order to go
Additional clarifier is needed except carbon monoxide.
It is reacted by the reaction of methanol production hydrogen by following reaction equations 1.
[reaction equation 1]
CH3OH+H2O=CO2+3H2Δ H=49.4kJ/mol (1)
CH3OH=CO+2H2Δ H=90.5kJ/mol (2)
CO+H2O=CO2+H2Δ H=-41.1kJ/mol (3)
As above-mentioned, while reaction using the reforming reaction of methanol by (1) of above-mentioned reaction equation 1, partially in high temperature
The lower reaction for generating (2).But the reaction of (1) and (2) is the endothermic reaction, needs lasting supply to carry out these endothermic reactions
To heat, and for reaction speed, it is necessary to while adjusting the catalyst temperature for generating reforming reaction.
In addition, carrying out the direct decomposition reaction of methanol in the case that the temperature of reactor is excessively high in the reaction of above-mentioned (2)
It, in the case where temperature is too low, is sent out with the back reaction of the reaction of above-mentioned (3) so that the carbonomonoxide concentration in product is got higher
The reaction speed decline of catalyst layer while unboiled water steam condenses, so that the conversion capacity of methanol fuel is reduced, it is therefore desirable to
Conscientiously the temperature of reforming section is maintained.
In order to solve this problem, it is described in Korean granted patent 10-0314829 for tieing up the temperature of reformer
It holds certain temperature and has the methanol reformer of dual pipe.But the methanol reformer has the drawback that reactor
Size is large-scale, the side of combustion catalyst not fully contact reforming catalyst on the whole, and combustion catalyst is not filled out
It fills in a pipe, but dispersed filler is to many places, to be difficult to effectively supply heat to reforming section.
In addition, in U.S.'s Pacific Northwest National Laboratory (Pacific North National Laboratory)
It describes in paper J.of Power source, 108 (2002) 21-27 by methanol while being used as burning fuel and fuel reforming
Small-sized methanol steam reforming device.But the small-sized methanol steam reforming device has the drawback that have 200mW
The lower output power of left and right, and for maintaining reaction temperature, the fuel i.e. quantity of methyl alcohol put into burner is more, from
And the entirety thermal efficiency is very low, is 5 to 10%.
While keeping the size of reactor to be small-sized therefore, it is necessary to constantly research and develop, the thermal efficiency and hydrogen conversion ratio are higher
Reactor.
<existing technical literature>
Patent document: Korean granted patent 10-0314829 (on November 02nd, 2001)
Non-patent literature: Pacific North National Laboratory, J.of Power source, 108
(2002)21-27
Summary of the invention
(1) technical problems to be solved
The present invention is to propose to solve the above-mentioned problems, and its purpose is to provide one kind for being produced by carbon compound
The heat exchange type reactor of hydrogen, the heat exchange type reactor can make required minimum energy consumption in phase transformation, simultaneously
It is adjacent to filling reforming catalyst and combustion catalyst across shell, minimizes heat transfer distance, thus, it is possible to simple
Structure manufacture at small-sized reactor.
It is further an object that a kind of hydrogen-manufacturing reactor is provided, by matching the part for evaporating liquid fuel
It sets and carrys out quick start reactor in inside reactor, thus, it is possible to the confessions rapid and stable to emergency power supply fuel cell
To hydrogen.
It is further an object that providing a kind of hydrogen-manufacturing reactor, which has been effectively removed by being carbonized
The carbon monoxide in the gas rich in hydrogen that object generates is closed, thus even if supplying as fuel into polymer fuel cell,
It will not lead to the deterioration of fuel cell.
(2) technical solution
The present invention relates to a kind of hydrogen-manufacturing reactors by carbon compound production hydrogen.
An aspect of of the present present invention is related to a kind of reactor, which is generated hydrogeneous by the raw material comprising carbon compound and water
Reformation gas, the reactor includes: reforming section, generates hydrogeneous reformation gas by reforming the raw material；Combustion section passes through
It burns the raw material and supplies heat to the reforming section；Heat feed line；And reformer feed phase transition tube, it is located at combustion section
It is interior, and raw material is heated, wherein successively it is separated by from outside with concentric structure and is provided with first shell, second shell and adds
Pyrogen material conveying tube, the reforming section and combustion section respectively by the first shell and the second shell be separated by space and
The second shell and the heating feed line are separated by space and are individually formed.
At this point, the reactor can have: reforming section, the first shell and being separated by space for the second shell fill out
Filled with reforming catalyst；And combustion section, the second shell and the heating are filled with being separated by space for feed line
Combustion catalyst.
Another aspect of the present invention relates to a kind of reactors comprising: reforming section includes carbon compound and water by reforming
Raw material generate hydrogeneous reformation gas；And combustion section, heat is supplied to reforming section by burning the raw material, wherein from
Interior is disposed with heating feed line, first shell and second shell with concentric circles, the reforming section by
The space that is separated by of first shell and second shell formed, and the combustion section is separated by sky by second shell and heating feed line
Between formed, include the reformer feed phase transition tube heated to raw material in the inside of the combustion section, the one of the reforming section
End includes carbon monoxide removal portion.
At this point, may be provided in second shell in the identical height and position adjacent with the carbon monoxide removal portion
The reformer feed phase transition tube of side.
In addition, the reactor can have: reforming section, the first shell and the second shell are separated by space filling
There is reforming catalyst；The end in carbon monoxide removal portion, the reforming section is filled with carbon monoxide removal catalyst；And burning
Portion, the second shell and the heating feed line are separated by space filled with combustion catalyst.
In the present invention, it can be also equipped with heater or combustion catalyst in the inside of the heating feed line, it is described to add
The lower end of pyrogen material conveying tube and the lower end of the second shell are spaced from each other and form first compartment, and the second shell
Lower end and the lower end of the first shell be spaced from each other and form second compartment.
In the present invention, the combustion catalyst can be filled from the lower end of the combustion section, and be filled into and the combustion section
Upper end, the inside lower end of the raw material phase transition tube and the inside lower end of the heater be spaced from each other, the reforming catalyst
It can fill from the lower end of the reforming section, and be separated with the upper end phase family of the reforming section.
In the present invention, the reactor can also have the heating raw material is defeated in the upper end of the heating feed line
The horizontal isolation board for sending pipe, the first shell and the second shell to be isolated from the outside, and it is defeated to may be configured as heating raw material
Send pipe, combustion products discharge pipe, reformer feed supply pipe and reformer feed discharge pipe through the horizontal isolation board.
In the present invention, the heating raw material supply pipe can be connect with the heating feed line, the combustion products
Discharge pipe can be connect with the combustion section, it is described state reformer feed supply pipe and reformer feed discharge pipe can respectively with the raw material
One end of phase transition tube connects, and the reformer feed discharge pipe can be connect by preheating pipe with the second compartment.
In addition, the preheating pipe connecting with the reformer feed discharge pipe can coat the first shell with coil shape
Side.
In addition, the space for being not filled with combustion catalyst in the combustion section can also have thermal conductive network, the reformation
Portion can also have more than one transfer pin of heat.
In the present invention, combustion catalyst, reforming catalyst or carbon monoxide removal catalyst may include selected from gold, silver, iron,
The metal of one or more of cobalt, nickel, copper, manganese, aluminium, zinc, titanium, hafnium, rhodium, ruthenium, osmium, iridium, palladium, zirconium and lanthanum race metal or they
Oxide, specifically, the combustion catalyst may include selected from one or more of platinum, rhodium, ruthenium, osmium, iridium, palladium, gold, silver and copper
Metal or their oxide, the reforming catalyst of stating may include selected from copper/cerium oxide/zirconia composite, copper/oxidation
It is more than any in zinc/alumina composite, copper/cerium oxide/alumina composite and copper/zirconium oxide/alumina composite
Complex.
In the present invention, raw material is stored in head tank, and the raw material may include being supplied from the head tank to the heating
Heating raw material in raw material supply pipe and the reformer feed into the reformer feed supply pipe is supplied from the head tank.
Another aspect of the present invention is the hydrogen production process using the hydrogen-manufacturing reactor, wherein heating raw material is by including
Following steps and flow: a) heat raw material by heat raw material supply pipe be delivered to heat feed line in；B) pass through first
Compartment is delivered to combustion section from the heating feed line of stating, and occurs with the combustion catalyst being filled into the combustion section
It reacts and carries out catalysis burning；And c) combustion products is expelled to by combustion products discharge pipe after catalysis burning
The outside of reactor, reformer feed are flowed and including the following steps: 1) reformer feed is conveyed by reformer feed supply pipe
Mutually become gas phase after into reformer feed phase transition tube；2) reformer feed of phase transformation passes through reformer feed discharge pipe and preheating pipe
And it is delivered in second compartment；3) reformer feed of the supply into the second compartment by reforming section and with filling to reforming section
In reforming catalyst react；And 4) product after reaction is expelled to the outside of reactor.
In addition, the present invention, which after the 3) step, may additionally include reforming section end, passes through carbon monoxide removal portion
Carbon monoxide removal catalyst layer simultaneously implements the step of selective carbon monoxide removal reacts.
In the present invention, the heating raw material or reformer feed may include the water and 50 to 70 weight % of 30 to 50 weight %
Carbon compound, reforming catalyst can maintain 100 DEG C to 300 DEG C of temperature range in the 3) step.It therefore, can will be pre-
Heat pipeline is arranged to wind downwards in a manner of the peripheral contacts with first shell.
The scheme recorded above is not limited to documented content, including those skilled in the art can be easy to replace
All items changed.As an example, include the case where the device that other way is used for the purpose of implementing identical technology.
(3) invention effect
Heat exchange type reactor according to the present invention for by carbon compound production hydrogen, from outside successively with Heart-to-Heart
Structure, which is separated by, is provided with first shell, second shell and heating feed line, to being separated by by each shell and feed line
And combustion catalyst or reforming catalyst are filled in the space generated respectively, thus, it is possible to will be catalyzed the heat that burning generates to be easy transmitting
Thermal gradient is freely adjusted into reforming catalyst, and according to the filling situation of catalyst.
Carbon monoxide removal portion is configured in one end of reforming section in particular, having the advantages that, so as to drastically reduce
Carbonomonoxide concentration, and by the way that the heat generated by the carbon monoxide removal portion is transmitted to adjacent heating feed line
In and while system heat is efficiently used, can be steadily in the long term using the catalysts in carbon monoxide removal portion.
In addition, internal be configured with raw material phase transformation portion, being catalyzed the heat that burning generates by supply makes energy required for phase transformation
Amount consumption minimizes, and can start reactor rapidly under the state of cooling, therefore very economical, and can reduce the big of reactor
It is small to keep its compact-sized.
In addition, being carried out by the way that the heater inside heating feed line is arranged in heating fuel in initial launch
Gasification, and be supplied in combustion catalyst together with air, then under liquid phase feed and the discontiguous situation of combustion catalyst
It is able to carry out stable combustion reaction, when combustion reactor starting, combustion products is to setting in heating feed line
The reformer feed phase transition tube of upper end is heated, and makes to be supplied to the liquid reformer feed gasification in reforming catalyst.Therefore, have
Following advantage: can also successively gasify rapidly to heating raw material and reformer feed by simple structure and it is each to be supplied to
In a catalyst layer.
In the case where heat exchange type reactor of the invention is connected with fuel cell, can be used by advantage as described above
Make the substitute of backup battery or lead storage battery, come be widely used in not only using hydrogen as in the general energy system of fuel but also
In terminating machine, repeater on out-of-the-way ground for being difficult to supply electric power etc..
Detailed description of the invention
Fig. 1 to Fig. 6 is the figure for showing the section of reactor of one embodiment of the present of invention.
Fig. 7 is the figure for showing the section of reactor of internal removal heating feed line.
Fig. 8 is the figure for showing the section for the horizontal isolation board for having heating feed line and reformer feed phase transition tube.
Fig. 9 and Figure 10 is the figure for showing the section of heating feed line and reformer feed phase transition tube.
Figure 11 is the figure for showing the lower end for the reformer feed phase transition tube being made of coiled coil.
Figure 12 is the plan view for showing horizontal isolation board.
Description of symbols
1: reactor 2: first shell
3: second shell 4: horizontal isolation board
5: reforming section 6: reforming catalyst
7: combustion section 8: combustion catalyst
9: carbon monoxide removal portion 10: heating feed line
11: reformer feed phase transition tube 12: heating raw material supply pipe
13: combustion products discharge pipe 14: reformer feed supply pipe
15: reformer feed discharge pipe 16: preheating pipe
17: first compartment 18: second compartment
19: thermal conductive network 20: transfer pin of heat
21: flange 22: bolster
23: guidance punched-plate 24: reforming and generate gas outlet pipe
25: heater
Specific embodiment
In the following, being said in more detail using attached drawing and concrete example to the reactor of the invention by carbon compound manufacture hydrogen
It is bright.But example or embodiment are only to be used for the reference that the present invention will be described in detail in detail below, the present invention is not limited to
This, can realize in many ways.
In addition, if then all technical terms and scientific words have leads with technology belonging to the present invention without other definition
The identical meaning of meaning that some technical staff in the technical staff in domain are commonly understood by.It uses used in the explanation of the invention
Language is only used for effectively describing specific embodiments, is not intended to limit the invention.
In addition, attached drawing introduced below is provided to sufficiently convey thought of the invention to those skilled in the art
's.Therefore, the present invention is not limited to the following drawings, can also be embodied in other forms, in order to clearly of the invention
Thought can amplify the attached drawing for indicating set forth below.In addition, identical appended drawing reference refers to identical composition in the specification
Component.
In addition, the singular used in specification and claims, if do not referred to particularly in article
Show, then the singular also may include plural form.
About reactor of the invention, in Fig. 1 by the reformation in one end of reactor one locating for raw material supply pipe
End is referred to as " upper end ", and the other end opposite with upper end is referred to as " lower end ".This, but also can be to first shell not only to reactor
Body, second shell and feed line are applicable in above-mentioned identical top and bottom.
Term used in the present invention " concentric shafts " refers to when the direction observing response device for flowing into the reactor from raw material
When, connect the axis that the first shell, second shell and feed line are formed by centre of figure.At this point, the figure
Center indicates center of gravity, and the first shell, second shell and feed line are also possible to identical or different shape.In addition,
On the basis of the direction perpendicular to the concentric shafts, from the first shell, second shell and feed line with concentric shafts
Opposite direction indicates internal, and opposite direction indicates external.
Term used in the present invention " raw material " is to be referred to as liquid phase or gaseous substance comprising carbon compound and water, the raw material
It is stored in head tank, the raw material may include " the heating original supplied from the head tank to the heating raw material supply pipe
Material " and " reformer feed " supplied from the head tank to the reformer feed supply pipe.In addition, the heating raw material and again
Whole raw material also can have identical or different ratio of components, and the present invention is not limited thereto.
Fig. 1 to Fig. 3 is the cross-sectional view of the hydrogen generation reactor of one embodiment of the invention.As shown in Figure 1 to Figure 3, originally
The reactor of invention has first shell, second shell and the feed line of concentric structure, and the first shell, second
Shell and feed line are provided spaced.In addition, inside is further equipped with reformer feed phase transition tube, thus in single reaction
Conveying, phase transformation, burning and the reforming reaction of raw material can be carried out in device simultaneously.
This is described in more detail, the reactor 1 is sealed by first shell 2 and horizontal isolation board 4, described
The inside of reactor 1 has second shell 3, heating feed line 10 and reformer feed phase transition tube 11.In addition, being isolated in level
Heating raw material supply pipe 12 is provided on plate in a manner of penetrating through horizontal isolation board 4 respectively, combustion products discharge pipe 13, is reformed
Raw material supply pipe 14 and reformer feed discharge pipe 15, internally to supply reformer feed or heating raw material outside reactor, or
Product is discharged from inside reactor to outside after the reaction.
For the heating raw material supply pipe 12 for that will heat feedstock transportation into heating feed line 10, the heating is former
Material can carry out catalysis burning by the combustion catalyst 8 being laminated in the combustion section, and product passes through after catalysis burning
Combustion products discharge pipe 13 is discharged to outside reactor.
Furthermore it is possible to be supplied with the heating raw material being supplied in the heating feed line 10 independently by reformer feed
Reformer feed is supplied in reformer feed phase transition tube 11 to pipe 14.At this point, reformer feed phase transition tube 11 can be coil shape,
Can be expelled to by reformer feed discharge pipe 15 outside reactor by the reformer feed of the reformer feed phase transition tube 11 and with
Preheating pipe 16 is connected and is transported in the second compartment 18 of lower end.The reformer feed of conveying is fed into second compartment 18
And while reforming catalyst 6 by being laminated to inside reforming section, it is converted into the reformation gas rich in hydrogen and is discharged to reaction
Outside device.
In the present invention, first shell 2 and second shell 3 are metal material and have a concentric shafts, the first shell 2 and the
Two shells 3 can be provided spaced and form reforming section 5.In addition, can be filled with reforming catalyst 6 in reforming section.That is, as schemed
Shown in 2, the diameter of the first shell 2 is greater than the diameter of second shell 3, and the first shell 2 can have with by described second
The shape that the side of shell and the external mode separated completely surround.Furthermore, it is possible to surround second shell with reforming catalyst 6
The mode of a part in side is arranged.
The reforming section 5 is the position that reformer feed is converted into the gas containing hydroforming by reforming reaction, described to state reformation
A part in portion 5 can be filled with reforming catalyst 6, can be formed with the original after discharge is reformed in the upper end of the reforming section 5
The outlet of material.
In addition, reactor 1 of the invention can have the lower end of first shell and the lower end of the second shell to separate and shape
At the structure of second compartment 18.The second compartment plays the flow path for receiving gaseous fuel reforming and being delivered to the reforming section
Effect.
The lower end of the reforming section 5 can have guidance punched-plate 23, to be easy filling reforming catalyst 6.The guidance punching
Orifice plate 23 also has other than having the function of preventing the reforming catalyst 6 from falling or dispersing to the second compartment 18
Separate the function at the interval between the reforming section and the second compartment 18.In addition, the guidance punched-plate 23 can have net
Hole shape or hollow shape, so that the reformer feed easily flows into reforming section, but the present invention is not limited to this.
Preferably, the reforming catalyst 6 is filled from the lower end of reforming section, and the point on the basis of the guidance punched-plate 23
Filling is separated with the upper end of the reforming section.Reforming catalyst and the standoff distance of reforming section do not limit in the present invention, excellent
Selection of land maintains standoff distance across guide part and the reforming section identically as the lower end of the reforming section, it is highly preferred that described
The packed height of reforming catalyst 6 is higher than the packed height of combustion catalyst 8.
In the present invention, the heating feed line 10 can be located at the inside of the second shell 3, and have and first shell
Body 2 and the identical concentric shafts of second shell 3.In addition, second shell and heating feed line 10 can be spaced from each other and form combustion
Burning portion 7 can be filled with combustion catalyst 8 in the combustion section.
The combustion section 7 is that heating material combusting is made to be converted into thermal energy and combustion products by catalyst combustion reaction
Position, a part in the combustion section 7 can be filled with combustion catalyst, and former by the first compartment 17 of lower end and heating
Material conveying tube 10 connects, to receive heating raw material.In addition, the upper end being in contact with horizontal isolation board 4 can with run through the water
Flat isolation board and the combustion products discharge pipe 13 that is arranged connects.
As shown in Figure 1 to Figure 3, the combustion catalyst 8 can make to fill out according to the temperature range of reforming section and temperature gradient
Fill position and loading difference.It as an example, as shown in Fig. 2, can be straight by reducing the lower end of heating feed line 10
Diameter and the loading for being filled into the combustion catalyst of combustion section lower end is gradually increased, or as shown in figure 3, heating feed line
Lower end further fill combustion catalyst.This temperature for being used to make up reforming section lower end fails temperature required for reaching and makes
Reforming reaction is slow, and filling position and packed height can freely be adjusted according to the temperature of reforming section, the present invention is not limited to
This.
In addition, thermal conductive network 19 can be further imported in addition to the combustion catalyst in the combustion section 7, with more effectively
Pass through the heat of catalyst combustion reaction generation.The thermal conductive network can be by will such as gold, silver, copper, the higher gold of aluminium thermal conductivity
Belong to drawing fiber shape and weaves and formed.The thermal conductive network has the advantages that can be by will generate after catalyst combustion reaction
The heat for failing to transmit in time is transferred to reforming section, so as to improve energy to while external discharge rapidly by reaction product
Amount efficiency.
The thermal conductive network 19 can be located in the combustion section is not filled with the part of combustion catalyst, it is preferable that can be with
It is located at part locating for the raw material phase transition tube in the combustion section in a manner of surrounding raw material phase transition tube.
The heating feedstock transportation that the heating feed line 10 plays the role of to be externally entering is described to combustion section
Heating feed line 10 can be formed by the material identical or different with the first shell 2 or second shell 3.In addition, can lead to
The lower end and the lower end of the combustion section and the lower end of the second shell for crossing heating feed line be separated by and formed first every
Room 17.
In the present invention, the reformer feed phase transition tube 11 is led in order to which the reformer feed is mutually become liquid phase from gas phase
Enter, as shown in Fig. 1 to Fig. 3 and Fig. 9, the reformer feed phase transition tube 11 may be configured as coating the heating original with coil shape
The lateral surface of material conveying tube 10.
The present invention can further import heater 25, with the aqueous-phase reforming being fed into the reformer feed phase transition tube 11
Raw material mutually becomes gas phase.The position for stating heater 25 may be disposed at the upper end of the heating feed line 10, that is, described
The position that the heating feed line 10 and the heating raw material supply pipe 12 in heating feed line 10 connect.
The heater 25 winds the heating feed line 10 with the reformer feed phase transition tube 11 with coil shape
Face be oppositely arranged, so as to effectively supply heat to the reformer feed phase transition tube 11.
In the present invention, as shown in Fig. 1 to Fig. 3 and Figure 12, the horizontal isolation board 4 is for making the first shell 2, second
Shell 3 and heating feed line 10 are isolated from the outside, and heat raw material supply pipe 12, combustion products discharge pipe 13, again
Whole raw material supply pipe 14 and reformer feed discharge pipe 15 run through the horizontal isolation board 4 along the direction parallel with the concentric shafts.
In the present invention, the horizontal isolation board 4 can be bonded by the first shell 2 and flange 21.As a result, without with
Second shell 3 or heating feed line 10 bond respectively, can shorten built-up time.
In the present invention, the heating supply pipe 12 can be connect with the heating feed line 10, the combustion products
Discharge pipe 13 can be connect with the combustion section 7, the reformer feed supply pipe 14 and reformer feed discharge pipe 15 can respectively with institute
The one end for stating reformer feed phase transition tube 11 is connected with the other end.Since each pipe is connect with inside reactor, so as to guide
Product after heating raw material, reformer feed and reaction makes it effectively supply and be discharged.
In addition, the present invention will reform former to more effectively adjust the temperature gradient of the reforming section according to reformer feed
Material discharge pipe 15 is connect with preheating pipe 16, and the side that the preheating pipe 16 can coat reforming section 5 with coil shape is (outer
Wall).Cladding preheating pipe 16 guides heat exchange on its outer wall by the position for being possible to generate overheat in reforming section, by
This can adjust the temperature gradient of reforming section.
In the present invention, if the preheating pipe 16, which can be realized, transmits heat by the side for coating the reforming section 5
Purpose, then do not limit position, the number of turns of winding etc., and the preheating pipe 16 can also be with the direct phase of the reforming section 5
It contiguously winds or is wound at spaced intervals with the reforming section 5.
In addition, as shown in figure 8, transfer pin of heat 20 can be further equipped in the reforming section of reactor 1 of the invention, with pass through by
In reforming section heat on the whole Transmit evenly and further increase the thermal efficiency.The position of the transfer pin of heat is not limited in the present invention
It sets, shape, size, material etc., but preferably, may be configured as not interfere the type of flow of reformer feed to pass through heat transfer pin connection
Material identical with first shell and second shell can be used in the material of the first shell and second shell, the transfer pin of heat.
Reforming section 5 is described in the explanation of above-mentioned attached drawing, and space shape is separated by by first shell and second shell
At, and it is internal be filled with reforming catalyst 6, combustion section 7 is separated by space by second shell and the heating feed line
And it is formed, and internal filled with combustion catalyst 8, but the reforming section and combustion section also can be interchanged position and be arranged.That is, institute
Stating reforming section can be formed by the space that is separated by of second shell and the heating feed line, and be located inside reactor,
The combustion section can be formed by the space that is separated by of first shell and second shell, and using first shell as boundary and reactor
Outside connect.The type and carrying of the type of this carbon compound according to included in raw material, reformation or combustion catalyst
Generated calorific value etc. is adjusted when metal, burning, and the present invention is not limited to this.
Fig. 4 to fig. 6 is the cross-sectional view of the hydrogen generation reactor of another embodiment of the present invention.It can save in the following description
Slightly with the duplicate content of content described in above-mentioned Fig. 1 to Fig. 3.
As shown in Figures 4 to 6, reactor of the invention is characterized in that having carbon monoxide removal in reforming section downstream
Portion, the carbon monoxide removal portion are for being fed into reformer feed in second compartment 18 and by being laminated to reforming section 5
It is converted into after the reformation gas rich in hydrogen while reforming catalyst 6 of inside, removes contained carbon monoxide.That is, its
It is characterized in that, further comprises carbon monoxide removal portion 9, the carbon monoxide removal in the reactor of Fig. 1 above-mentioned to Fig. 3
Portion 9 is mutually become the rear end removal of the gas rich in hydrogen rich in the gas of hydrogen while reformer feed passes through reforming catalyst
Carbon monoxide.
The carbon monoxide removal portion 9 has the catalyst that can remove carbon monoxide.The method of removal carbon monoxide does not have
There is very big limitation, it is preferable that the selective methanation reaction such as following reaction equations 2 can be implemented.
[reaction equation 2]
CO+3H2→CH4+H2O (fever, the methanation of carbon monoxide) (4)
CO2+4H2→CH4+2H2O (fever, carbon dioxide methanation) (5)
CO2+H2→CO+H2O (heat absorption, reverse water-gas-shift reaction) (6)
In above-mentioned reaction equation 2, (4) indicate main reaction, carry out methanation to carbon monoxide, and generate and urge because of reaction
Fever in agent layer.On the contrary, (5) and (6) indicate side reaction, in the case where (6), coal against the current can be generated by the endothermic reaction
Gas conversion reaction.Sizable reaction heat can be generated in carbon monoxide removal portion as a result, improve the temperature of catalyst layer, together
(5), (6) of the Shi Jinhang as side reaction, it is possible to reduce the methanation conversion ratio and selectance of carbon monoxide.
In particular, as shown in Figure 10 and Figure 11, the reformer feed phase transition tube 11 of the reactor including carbon monoxide removal portion 9 is logical
It crosses coiled coil i.e. primary coil (inside) and secondary coil (outside) and connects, the reformer feed phase transition tube 11 has secondary
Shape of the coil around the outer peripheral surface of primary coil.At this point, the secondary line corral of a part as reformer feed phase transition tube 11
While around heating feed line 10, second shell is being surrounded across the second shell position opposite with carbon monoxide removal portion 9
The medial surface of body 3, so that it is adjacent with carbon monoxide removal portion 9, thus the heat that carbon monoxide removal portion 9 generates can be moved to weight
In whole raw material phase transition tube 11.That is, passing through the portion for making the carbon monoxide removal portion 9 be located at and be formed with reformer feed phase transition tube 11
The similar position of height divided makes the i.e. selective methane of the exothermic reaction generated by the latent heat of the reformer feed phase transition tube 11
Changing reaction has certain temperature range, so that the thermal gradient in carbon monoxide removal portion adjusts easiness and catalysts
It is more advantageous in terms of stability.This is able to maintain that certain temperature, to prevent the temperature of the catalysts because of carbon monoxide removal portion 9
It spends high and side reaction or catalyst is caused to damage.
Preferably, the catalyst layer in the carbon monoxide removal portion can have 200 to 300 DEG C of temperature range.Meeting
In the case where above range, the methanation transformation efficiency of carbon monoxide is higher, can use carbon monoxide removal steadily in the long term
Catalysts in portion 9.
The reactor of the reactor of fig. 4 to fig. 6 Fig. 1 as the aforementioned to Fig. 3 is the same, and first shell 2 and second shell 3 are gold
Belong to material, and there are concentric shafts, first shell 2 and second shell 3 are spaced from each other and form reforming section 5, in the reforming section 5
Upper end can be formed with the outlet for the raw material discharge after reforming.But the weight being filled into the reforming section 5 is shown in attached drawing
Whole catalyst 6 is located at position identical with reforming section 5, and but it is not limited to this, it is thus understood that reforming catalyst 6 is filled into reforming section
In 5.In addition, the end for being commonly referred to as the reforming section 5 is connect with carbon monoxide removal portion 9.
In the present invention, reforming catalyst 6 may include being selected from gold, silver, iron, cobalt, nickel, copper, manganese, aluminium, zinc, titanium, hafnium, rhodium, ruthenium,
The metal or their oxide of one or more of osmium, iridium, palladium, zirconium and lanthanum race metal.Specifically, the reforming catalyst
6 may include selected from copper/cerium oxide/zirconia composite, copper/zinc oxide/alumina complex, copper/cerium oxide/alumina composite
Any above complex in body and copper/zirconium oxide/alumina composite.
In more detail, can be used copper: zinc: aluminum oxide presses Co deposited synthesis with 3 to 5:3 to 5:1 to 3 weight ratio
Complex, but it is not limited to this.
In the present invention, the combustion catalyst 8 may include selected from gold, silver, iron, cobalt, nickel, copper, manganese, aluminium, zinc, titanium, hafnium,
Rhodium, ruthenium, the metal or their oxide of one or more of osmium, iridium, palladium, zirconium and lanthanum race metal, it is preferable that can be and be selected from
Such as platinum (platinum), rhodium (rhodium), ruthenium (ruthenium), osmium (osmium), iridium (iridium) and palladium
(palladium) platinum family element, gold, silver, copper or the group being made of mixture more than two of which such as.
In addition, the combustion catalyst 8 can be used in the carrier by carrying.It can be as the carrier selected from oxygen
Change aluminium, Alpha-alumina, zirconium dioxide (ZrO2), silica (silica；SiO2) or by the above mixture structure of two of which
At group in more than one.In addition, not limiting the physical properties such as shape of particle, the size of carrier, can also not interfere
It freely adjusts in the range of the object of the invention to use.
In addition, the combustion catalyst 8 can adjust holding for metal or metal oxide according to the temperature gradient of reforming section
Carrying capacity.That is, the case where not can ensure that temperature required for reaction by the reforming section temperature after measurement catalyst combustion reaction
Under, can be improved the metal of the combustion catalyst or the bearing capacity of metal oxide, and can by the temperature in reforming section compared with
The more combustion catalyst of bearing capacity is filled in low segment set to adjust temperature required for meeting reforming reaction.
In the present invention, it is preferable that the carbon monoxide removal catalyst that 9 inside of carbon monoxide removal portion has can wrap
Containing selected from one of gold, silver, iron, cobalt, nickel, copper, manganese, aluminium, zinc, titanium, hafnium, rhodium, ruthenium, osmium, iridium, palladium, zirconium and lanthanum race metal with
On metal or their oxide, but not limited to this.
In the following, the present invention is described in more detail based on fluid travel path.
The heating raw material is flowed and including the following steps:
A) it is delivered in the heating feed line 10 by the heating raw material supply pipe 12；
B) be delivered in the combustion section 7 by the first compartment 17 from the heating feed line 10, and with fill out
The combustion catalyst 8 being charged in the combustion section reacts, and carries out catalysis burning；And
C) combustion products is discharged to by reactor 1 by the combustion products discharge pipe 13 after catalysis burning
Outside,
The reformer feed is flowed and including the following steps:
1) reformer feed mutually becomes gas phase after being delivered in reformer feed phase transition tube by reformer feed supply pipe；
2) reformer feed of phase transformation is transported in second compartment by reformer feed discharge pipe and preheating pipe；
3) reformer feed being supplied in the second compartment passes through reforming section and urges with the reformation being filled in reforming section
Agent reacts；And
4) product after reaction is expelled to outside reactor.
In addition, the present invention can further comprise passing through carbon monoxide removal in reforming section end after above-mentioned 3) step
The carbon monoxide removal catalyst layer in portion simultaneously implements the step of selective carbon monoxide removal reacts, and carbon monoxide is gone
Except product after reaction is discharged to outside reactor.
Specifically, each firstly, the reformer feed and the heating raw material of stating are stored in head tank (not shown)
Raw material also can have identical or different composition.The raw material may include the water and 50 to 70 weight % of 30 to 50 weight %
Carbon compound can be according to composition, the temperature gradient adjusting condition of reforming section etc. of catalyst about the content of the carbon compound
Freely change ratio of components.
In the present invention, the carbon compound may include in this field as purposes such as organic synthesis material, solvent, detergent
Come alcohol, aldehyde, ketone, the ester etc. used, the alcohol can enumerate the low orders alcohol such as ethyl alcohol, butanol in addition to methanol, in addition to this,
The ketone of aldehyde, acetone, butanone, pentanone of formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde etc. etc. can be used.But with the carbon compound
Carbon amounts increase, the impurity such as carbon deposition based on reformation also increase, to need accurate adjustment running temperature, therefore can also be excellent
Choosing uses methanol.
The water comes usually as solvent using so as to use pure water, and in order to save energy and improve reaction
Carry out speed, warm can also be passed through.In the present invention, such as a) and b) step, firstly, the heating fuel pass through it is described
Heating raw material supply pipe 12 is delivered in the heating feed line 10, and is injected into the inside of reactor 1, adding after injection
Hot charge can be delivered in the combustion section 7 via heating feed line 10, first compartment 17.That is, working as the heating raw material
It, can when via first compartment 17 and by the combustion section 7 by entering when heating feed line 10 from upper end to lower end
It is carried out from combustion section lower end to upper end.
Catalysis burning is is adsorbed, is moved, reacts and generate catalyst surface layer is compound by heating fuel
Oxidation reaction, have the advantages that can also to stablize at a lower temperature due to lower active-energy and carry out combustion reaction.
Further, since efficiency of combustion is higher, product can be analyzed to nontoxic, tasteless carbon dioxide and oxygen after reaction, there is no need into
The secondary treatment of row wastewater treatment etc., the thermalization speed for being able to suppress combustion catalyst increase.
Heating fuel after reaction is converted into carbon dioxide and water, and as above-mentioned c) step, passes through burning
Product discharge pipe 13 is to being discharged outside reactor.
In the present invention, the reformer feed may travel to lower step: firstly, 1) defeated by the reformer feed supply pipe 14
Send to the raw material phase transition tube 11, then, 2) reformer feed is mutually become into gas phase.
In the present invention, the reformer feed can be supplied with liquid phase, but can also be with according to technique and the structure of reactor
Gas phase supply.In more detail, it is 1. heated after being supplied with liquid phase with heater 25 and carries out phase transformation in inside reactor,
Or 2. carry out phase transformation in advance before being injected into reactor 1, it is then supplied in reactor.Although alternatively, being supplied to liquid phase
In reactor, but 3. first heating raw material can also be supplied into reactor, and burnt by catalysis and receive heat, to react
Phase transformation is carried out inside device.
Preferably, inside reactor carry out initial catalyst combustion reaction in the case where, stop heater 25 operation with
Save energy.This is because as described above, by the catalyst combustion reaction to reactor sustainable supply heat, thus the liquid
By spontaneous vaporization while phase reforming catalyst passes through raw material image converter tube 11.
After reformer feed after phase transformation is expelled to outside reactor by the reformer feed discharge pipe 15, via preheating
Pipeline 16 is moved in second compartment 18.At this point, being reformed as described above, can be wound by the preheating pipe 16 with coil shape
The outside in portion (5) adjusts the temperature gradient of reforming section.
Being moved to the reformer feed in second compartment can be flowed into reforming section 5 via guidance punched-plate 23, and carry out
State 4) step.In the reforming section, hydrogen, carbon dioxide, an oxygen can be converted by reformer feed by reforming catalyst 6
Change carbon and methane etc..
The reaction of reformer feed and reforming catalyst 6 is carried out by following reaction equations 1, and (2) of reaction equation 1 are the direct of methanol
Decomposition reaction can locally generate the decomposition reaction at high temperature.
[reaction equation 1]
CH3OH+H2O=CO2+3H2Δ H=49.4kJ/mol (1)
CH3OH=CO+2H2Δ H=90.5kJ/mol (2)
CO+H2O=CO2+H2Δ H=-41.1kJ/mol (3)
In above-mentioned 4) step, the temperature for the reforming catalyst being laminated in reforming section 5 can be 100 DEG C to 300 DEG C.?
In the case that temperature is less than 100 DEG C, it is unable to fully energy required for obtaining reforming reaction, so that carbon monoxide is converted into hydrogen
Conversion ratio be greatly reduced, more than 300 DEG C, due in product carbon monoxide content increase, to be difficult to
Remove carbon monoxide, and it is possible to sharply generate the thermal denaturation of reforming catalyst.
Product after carrying out reforming reaction can be before generating gas outlet pipe 24 by reformation and being expelled to outside, removal
It is supplied in fuel cell after carbon monoxide.At this time, it is preferable that the reformation after removal carbon monoxide generates the intracorporal oxygen of gas
Change concentration of carbon in 10ppm or less.
Specifically, following method can be used in the method for removing carbon monoxide contained in the product: utilizing
Generate the reaction of selective Oxidation of Carbon Monoxide or the selectivity the methanation of carbon monoxide of reaction shown in reaction equation 3 or reaction equation 4
Reaction, makes carbon monoxide be converted into carbon dioxide or methanol.
[reaction equation 3]
CO+1/2O2→CO2
Above-mentioned reaction equation 3 is to supply air to provide the oxygen reacted with carbon monoxide, and pass through reformation gas
Uniform mixing with air and induce effective Oxidation of Carbon Monoxide to react.Therefore, for being selectively oxidized the stream of reaction
Line structure is complicated, it is difficult to be safeguarded.
It is thus preferable that can further include carbon monoxide removal catalyst in carbon monoxide removal portion, make it possible to reality
Apply the reaction of selectivity the methanation of carbon monoxide shown in reaction equation 4.But the present invention is not limited to the selective carbon monoxide
Methanation reaction.
[reaction equation 4]
CO+3H2→CH4+H2O
In the following, the present invention will be explained in more detail by way of examples.But following embodiment is only used for being described in detail
Example of the invention, the present invention is not limited thereto.
Embodiment 1
The copper being fabricated as the tray shape with average diameter for 1.5mm of reforming catalyst is filled in reforming section
(Cu) constituent catalysts are filled with platinum (Pt) catalyst being fabricated with ceramic honeycomb (honeycomb) shape in combustion section.
Preheating pipe uses 1/8 inch pipe, and according to height reforming section is externally wrapped with into coiled type at equal intervals, to make to gasify
Reformer feed by outer wall reforming section supply heat further preheating.
Raw material used methanol by mixing 60 weight % on the basis of quality and 40 weight % distilled water and make
Liquid fuel.In addition, heating raw material and reformation use identical liquid fuel with raw material.As reformer feed, with 7.8g/
Min supplies the liquid fuel.Raw material is heated to supply with the flow of 2.9g/min, in order to burn, withFlow velocity it is same
When supply air, so that the maximum temperature for adjusting reforming section catalyst layer is maintained at 280 DEG C or less.At this point, using gas chromatograph
It analyzes the composition of the product after reforming, and is documented in table 1.Group in bracket, which becomes, to be calculated at 250 DEG C of reaction temperature
Equilibrium composition value.Reach 96% by the calculated methanol conversion of carbon amounts conservation formula, the production hydrogen flowing quantity of calculating is
0.52Nm3/h。
[table 1]
Embodiment 2
The copper being fabricated as the tray shape with average diameter for 1.5mm of reforming catalyst is filled in reforming section
(Cu) constituent catalysts come, and platinum (Pt) catalysis being fabricated with ceramic honeycomb (honeycomb) shape is filled in combustion section
Agent.Preheating pipe uses 1/8 inch pipe, and according to height reforming section is externally wrapped with into coiled type at equal intervals, to make
The heat further preheating that the reformer feed of gasification is supplied by outer wall reforming section.In addition, the carbon monoxide in reforming section end is gone
Except portion is filled with the catalyst of ruthenium (Ru) ingredient that the tray shape with average diameter for 1.5mm is fabricated.
Raw material makes and having used the distilled water of methanol and 40 weight % by mixing 60 weight % on the basis of quality
Liquid fuel.In addition, heating raw material and reformation use identical liquid fuel with raw material.As reformer feed, with 7.8g/
Min supplies the liquid fuel.Raw material is heated to supply with the flow of 2.9g/min, in order to burn, withFlow velocity it is same
When supply air, so that the maximum temperature for adjusting reforming section catalyst layer is maintained at 280 DEG C or less.At this point, using gas chromatograph
It analyzes the composition for the product reformed and is documented in table 2.The content of carbon monoxide is 10ppm hereinafter, based on carbon amounts conservation formula
The methanol conversion of calculating reaches 95% or more, and the production hydrogen flowing quantity of calculating is 0.50Nm3/h。
[table 2]
Above preferred embodiments of the present invention have been disclosed for illustrative, but the present invention may include a variety of variations and change and be equal
Object, and can be by suitably being deformed to above-described embodiment.Therefore, above-mentioned contents are not limited based on claims
Restriction come the scope of the present invention that determines.
Claims (22)
1. a kind of reactor, comprising: reforming section generates hydrogeneous weight by reforming the reformer feed comprising carbon compound and water
Whole gas, and it is filled with reforming catalyst；And combustion section, heat is supplied to reforming section by combustion heating raw material, and fill out
Filled with combustion catalyst, wherein
Portion is disposed with heating feed line, first shell and second shell with concentric structure from the inside,
The reforming section is formed by the space that is separated by of first shell and second shell, and the combustion section is former by second shell and heating
The space that is separated by of material conveying tube is formed, the reforming catalyst being filled in the reforming section and the combustion being filled in the combustion section
It is adjacent across the second shell to burn catalyst,
The lower end closed of the second shell, therefore the reforming section is not connected to mutually with the combustion section,
The lower end and the lower end of the second shell of the heating feed line are spaced from each other and form first compartment, and described the
The lower end of two shells and the lower end of the first shell are spaced from each other and form second compartment,
The heating feed line is connected with each other by the first compartment and the combustion section, thus heats raw material from described
Heating feed line is supplied to the combustion section, and the heating raw material supplied from the heating feed line is in the combustion
The upward extreme direction flowing in lower end in burning portion from reactor,
The reformer feed is supplied by the second compartment to the reforming section, and in the reforming section under reactor
Upward extreme direction is held to flow,
Also, filled with burning in the combustion section adjacent with the lower end of the reforming section by second compartment supply reformer feed
Catalyst, the inside of the combustion section include reformer feed phase transition tube, coat the heating feed line with coil shape
And raw material is heated,
It also, further include heater or combustion catalyst in the inside of the heating feed line.
2. reactor according to claim 1, wherein
One end of the reforming section further includes carbon monoxide removal portion.
3. reactor according to claim 2, which is characterized in that
It further include in second shell in and the adjoining position opposite with the carbon monoxide removal portion across second shell
The reformer feed phase transition tube of side.
4. reactor according to claim 2, wherein
The reactor includes the carbon monoxide removal portion filled with carbon monoxide removal catalyst in the end of reforming section.
5. reactor according to claim 1, wherein
It is also equipped in the upper end of the heating feed line by the heating feed line, the first shell and the general
The horizontal isolation board that second shell is isolated from the outside.
6. reactor according to claim 5, wherein
The horizontal isolation board is set as heating raw material supply pipe, combustion products discharge pipe, reformer feed supply pipe and reformation
Raw material discharge pipe runs through the horizontal isolation board.
7. reactor according to claim 6, wherein
The heating raw material supply pipe is connect with heating feed line, and the combustion products discharge pipe is connect with combustion section,
The reformer feed supply pipe and reformer feed discharge pipe are connect with one end of reformer feed phase transition tube and the other end respectively.
8. reactor according to claim 7, wherein
The reformer feed discharge pipe is connect with the second compartment.
9. reactor according to claim 6, wherein
The reformer feed discharge pipe is connect with preheating pipe, and the preheating pipe is with the outside of coil shape cladding first shell
Face.
10. reactor according to claim 1, wherein
Part in the lateral surface of the first shell filled with reforming catalyst is also equipped with more than one temperature sensor.
11. reactor according to claim 1, wherein
The space that combustion catalyst is not filled by the combustion section is also equipped with thermal conductive network.
12. reactor according to claim 1, wherein
The reforming section is also equipped with more than one transfer pin of heat.
13. reactor according to claim 1, wherein
The combustion catalyst or reforming catalyst include selected from gold, silver, iron, cobalt, nickel, copper, manganese, aluminium, zinc, titanium, hafnium, rhodium, ruthenium,
The metal or their oxide of one or more of osmium, iridium, palladium, zirconium and lanthanum race metal.
14. reactor according to claim 13, wherein
The combustion catalyst include metal selected from one or more of platinum, rhodium, ruthenium, osmium, iridium, palladium, gold, silver and copper or they
Oxide.
15. reactor according to claim 13, wherein
The reforming catalyst includes to be selected from copper/cerium oxide/zirconia composite, copper/zinc oxide/alumina complex, copper/oxygen
Change any above complex in cerium/alumina composite and copper/zirconium oxide/alumina composite.
16. reactor according to claim 4, wherein
The carbon monoxide removal catalyst include selected from gold, silver, iron, cobalt, nickel, copper, manganese, aluminium, zinc, titanium, hafnium, rhodium, ruthenium, osmium,
The metal or their oxide of one or more of iridium, palladium, zirconium and lanthanum race metal.
17. according to claim 1 to reactor described in any one of 16, wherein
The raw material is stored in head tank, and the raw material includes to supply from the head tank into the heating raw material supply pipe
Heating raw material and supply the reformer feed into the reformer feed supply pipe from the head tank.
18. a kind of raw material reforming method using hydrogen-manufacturing reactor, to utilize the hydrogen manufacturing of the reactor described in claim 17
Method, wherein
Heating raw material is flowed and including the following steps:
A) heating raw material is delivered in heating feed line by heating raw material supply pipe；
B) be delivered in combustion section by first compartment from the heating feed line, and be filled in the combustion section
Combustion catalyst reacts and carries out catalysis burning；And
C) combustion products is expelled to outside reactor by combustion products discharge pipe after catalysis burning,
Reformer feed is flowed and including the following steps:
1) reformer feed mutually becomes gas phase after being delivered in reformer feed phase transition tube by reformer feed supply pipe；
2) reformer feed of phase transformation is delivered in second compartment by reformer feed discharge pipe and preheating pipe；
3) reformer feed of the supply into the second compartment by reforming section and with the reforming catalyst that is filled in reforming section
It reacts；And
4) product after reaction is expelled to outside reactor.
19. the raw material reforming method according to claim 18 using hydrogen-manufacturing reactor, wherein
The heating fuel or fuel reforming include the water of 30 to 50 weight % and the carbon compound of 50 to 70 weight %.
20. the raw material reforming method according to claim 18 using hydrogen-manufacturing reactor, wherein
In the 3) step, the reforming catalyst has 100 DEG C to 300 DEG C of temperature range.
21. the raw material reforming method according to claim 18 using hydrogen-manufacturing reactor, wherein
It further include passing through the carbon monoxide removal catalyst in carbon monoxide removal portion in reforming section end after the 3) step
Layer simultaneously implements the step of selective removal is reacted.
22. the raw material reforming method according to claim 21 using hydrogen-manufacturing reactor, wherein
In the 4) step, the carbon monoxide removal catalyst layer has 200 DEG C to 300 DEG C of temperature range.
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| KR1020160070831A KR101830954B1 (en) | 2016-06-08 | 2016-06-08 | Hydrogen production system including unit for removal of carbon monoxide |
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| CN109798508B (en) * | 2017-11-17 | 2020-11-03 | 韩国能量技术研究院 | Steam reformer integrated with raw material preheating unit and hydrogen production system including the same |
| CN107986232A (en) * | 2017-11-28 | 2018-05-04 | 四川亚联高科技股份有限公司 | The method of methanol preparing high purity hydrogen |
| CN110194437A (en) * | 2018-02-24 | 2019-09-03 | 北京联力源科技有限公司 | A kind of chemistry of fuel chain hydrogen generating system and method |
| CN110683512A (en) * | 2019-10-23 | 2020-01-14 | 张家港氢云新能源研究院有限公司 | Reaction material input mechanism matched with integrated reforming hydrogen production device |
| CN111533089B (en) * | 2020-04-30 | 2022-05-03 | 郑州帅先新能源科技有限公司 | Heater, reforming hydrogen production device and reforming hydrogen production method |
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| CN101432065A (en) * | 2006-03-17 | 2009-05-13 | Ifp公司 | Internal combustion exchanger reactor for endothermic reaction in fixed bed |
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