CN106276794A - Hydrogen-manufacturing reactor - Google Patents
Hydrogen-manufacturing reactor Download PDFInfo
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- CN106276794A CN106276794A CN201610483078.2A CN201610483078A CN106276794A CN 106276794 A CN106276794 A CN 106276794A CN 201610483078 A CN201610483078 A CN 201610483078A CN 106276794 A CN106276794 A CN 106276794A
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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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- 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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- 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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- 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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- 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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- 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
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- 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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- 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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- 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
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Abstract
The present invention relates to a kind of reactor being generated hydrogeneous reformation gas by the raw material comprising carbon compound and water, described reactor includes: reforming section, and by reforming, described raw material generates hydrogeneous reformation gas；Combustion section, by the described raw material of burning to above-mentioned reforming section supply heat；Carbon monoxide removal reacting part, removes the carbon monoxide in hydrogeneous reformation gas；Heating feed line；And reformer feed phase transition tube, it is positioned at combustion section, and raw material is heated, wherein, be separated by successively with concentric structure from outside be provided with the first housing, the second housing and heating feed line, described reforming section and combustion section respectively by described first housing and being separated by space and described second housing and described being separated by space of heating feed line of the second housing and be individually formed.
Description
Technical field
The present invention relates to a kind of hydrogen-manufacturing reactor, this hydrogen-manufacturing reactor is converted into hydrogeneous weight by reformation carbon compound
Whole gas is also supplied in fuel cell.In particular it relates to a kind of hydrogen-manufacturing reactor being produced hydrogen by carbon compound, this hydrogen manufacturing is anti-
Answering device is that the raw material gasified by the phase transformation portion of evaporation mixing carbon compound and the liquid charging stock of water is being filled with the weight of catalyst
Whole reacting part is converted into hydrogeneous reformation gas, in order to promote this reaction and with reforming reaction part from adjacent stream on set
Put combustion reaction portion, and inducing moiety liquid charging stock carries out combustion reaction on a catalyst, thus by the heat of combustion reaction generation
It is supplied in reforming reaction portion as reaction heat.
Background technology
In recent years, along with the increase of the attention rate to environmental problem, to the concern of the clean fuel with hydrogen as fuel and
Demand is also increasing.High molecular fuel battery system is as efficient TRT, and the operating temperature of this system is low and can
Quickly starting, if being therefore connected with suitable hydrogen gas supplying apparatus, then can act as multipurpose power supply device.
The carbon compound comprising methanol does not contains sulfur component and has the molecular structure of higher hydrogen/carbon-ratio characteristic, simultaneously
Being prone to mix with water, and be liquid under room temperature, normal pressure, therefore this carbon compound is the combustion easily stored with high-energy-density
Material.As one of method producing hydrogen by the carbon compound including methanol, develop steam reforming method, and
This steam reforming method is widely used.
In order to be carried out steam reforming reaction by carbon compound, it is necessary first to for making the carbon compound of liquid and the mixed of water
The gasifier of compound gasification, for the burner to reforming reactor supply heat and for making liquid fuels for combustion gasify
Gasifier, when supply to such as polymer fuel cell easy by the polymer fuel cell of carbon monoxide image in time, in order to go
Extra depurator is needed except carbon monoxide.
Reacted by following reaction equation 1 by the reaction of methanol production hydrogen.
[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 using the reforming reaction of methanol to react by (1) of above-mentioned reaction equation 1, part is at high temperature
The reaction of lower generation (2).But, the reaction of (1) and (2) is the endothermic reaction, needs persistently to supply to carry out these endothermic reactions
Give heat, and for reaction speed, it is necessary to regulation simultaneously produces the catalyst temperature of reforming reaction.
Additionally, in the case of the temperature of reactor is too high in the reaction of above-mentioned (2), carry out the Direct Resolution reaction of methanol
The back reaction of the reaction with above-mentioned (3), thus the carbonomonoxide concentration in product uprises, and in the case of temperature is too low, sends out
While raw water vapor condensation, the response speed of catalyst layer declines, thus the conversion capacity of methanol fuel reduces, it is therefore desirable to
Conscientiously the temperature of reforming section is maintained.
In order to solve this problem, record in Korean granted patent 10-0314829 for making the temperature of reformer tie up
Hold uniform temperature and possess the methanol reformer of dual pipe.But, this methanol reformer has the drawback that reactor
Size is large-scale on the whole, combustion catalyst the side of incomplete contact between reforming catalyst, and combustion catalyst is not filled out
Fill in a pipe, but dispersed filler is to many places, thus be difficult to effectively supply heat to reforming section.
Additionally, at U.S.'s Pacific Northwest National Laboratory (Pacific North National Laboratory)
Paper J.of Power source, has recorded in 108 (2002) 21-27 and methanol has been used simultaneously as burn fuel and fuel reforming
Small-sized methanol steam reforming device.But, this small-sized methanol steam reforming device has the drawback that possess 200mW
The relatively low output of left and right, and in order to maintain reaction temperature, put into the fuel in burner i.e. quantity of methyl alcohol more, from
And overall thermal efficiency is the lowest, it is 5 to 10%.
Accordingly, it would be desirable to constantly research and development keep the size of reactor be small-sized while, the thermal efficiency and hydrogen conversion ratio are higher
Reactor.
<prior art literature>
Patent documentation: Korean granted patent 10-0314829 (November 02 calendar year 2001)
Non-patent literature: Pacific North National Laboratory, J.of Power source, 108
(2002)21-27
Summary of the invention
(1) to solve the technical problem that
The present invention proposes to solve the problems referred to above, its object is to provide a kind of for being produced by carbon compound
The heat exchange type reactor of hydrogen, this heat exchange type reactor can make minimum energy consumption required in phase transformation, simultaneously
It is adjacent to across housing fill reforming catalyst and combustion catalyst, makes heat transfer distance minimize, it is possible to simply
Structure be manufactured into small-sized reactor.
It is further an object that provide a kind of hydrogen-manufacturing reactor, it is by joining the part of evaporation liquid fuel
Put and quickly start reactor at inside reactor, it is possible to the rapid and stable confession of emergency power supply fuel cell
To hydrogen.
It is further an object that provide a kind of hydrogen-manufacturing reactor, this hydrogen-manufacturing reactor effectively eliminates by carbonization
Carbon monoxide in the gas rich in hydrogen that compound generates, even if thus as fuel supply in polymer fuel cell,
Also the deterioration of fuel cell it is not result in.
(2) technical scheme
The present invention relates to a kind of hydrogen-manufacturing reactor being produced hydrogen by carbon compound.
An aspect of of the present present invention relates to a kind of reactor, and this reactor is generated hydrogeneous by the raw material comprising carbon compound and water
Reformation gas, described reactor includes: reforming section, by reform described raw material generate hydrogeneous reformation gas；Combustion section, passes through
Burn described raw material and to described reforming section supply heat；Heating feed line；And reformer feed phase transition tube, it is positioned at combustion section
In, and raw material is heated, wherein, it is separated by successively with concentric structure from outside and is provided with the first housing, the second housing and adds
Pyrogen material conveying tube, described reforming section and combustion section respectively by described first housing and described second housing be separated by space and
Being separated by space and be individually formed of described second housing and described heating feed line.
Now, described reactor can possess: reforming section, and described first housing and described being separated by space of second housing fill out
It is filled with reforming catalyst；And combustion section, described second housing and described being separated by space of heating feed line are filled with
Combustion catalyst.
Another aspect of the present invention relates to a kind of reactor, comprising: reforming section, comprises carbon compound and water by reformation
Raw material generate hydrogeneous reformation gas；And combustion section, by the described raw material of burning to reforming section supply heat, wherein, from
Interior is disposed with heating feed line, the first housing and the second housing with concentric circles, described reforming section by
The space that is separated by of the first housing and the second housing is formed, and described combustion section is separated by sky by the second housing and heating feed line
Between formed, include the reformer feed phase transition tube that raw material is heated in the inside of described combustion section, in the one of described reforming section
End includes carbon monoxide removal portion.
Now, can be provided with in the second housing at the identical height and position adjacent with described carbon monoxide removal portion
The reformer feed phase transition tube of side.
Additionally, described reactor can possess: reforming section, the space that is separated by of described first housing and described second housing is filled
There is reforming catalyst；Carbon monoxide removal portion, the end of described reforming section is filled with carbon monoxide removal catalyst；And burning
Portion, the space that is separated by of described second housing and described heating feed line is filled with combustion catalyst.
In the present invention, heater or combustion catalyst can be also equipped with in the inside of described heating feed line, described in add
The lower end of pyrogen material conveying tube and the lower end of described second housing are spaced from each other and form the first compartment, and described second housing
Lower end and the lower end of described first housing be spaced from each other and form the second compartment.
In the present invention, described combustion catalyst can be filled from the lower end of described combustion section, and fills into and described combustion section
The inside lower end of upper end, the inside lower end of described raw material phase transition tube and described heater be spaced from each other, described reforming catalyst
Can fill from the lower end of described reforming section, and separate with the phase family, upper end of described reforming section.
In the present invention, described reactor also can possess described in the upper end of described heating feed line that to add hot charge defeated
Send the horizontal division board that pipe, described first housing and described second housing are isolated from the outside, and it is defeated to may be configured as adding hot charge
Pipe, combustion products discharge pipe, reformer feed supply pipe and reformer feed discharge pipe is sent to run through described horizontal division board.
In the present invention, described in add hot charge supply Guan Keyu described in heat feed line connect, described combustion products
Discharge pipe can be connected with described combustion section, described in state reformer feed supply pipe and reformer feed discharge pipe can respectively with described raw material
One end of phase transition tube connects, and described reformer feed discharge pipe can be connected with described second compartment by preheating pipe.
Additionally, the preheating pipe being connected with described reformer feed discharge pipe can be coated with described first housing with coil shape
Side.
Additionally, the space being not filled with combustion catalyst in described combustion section also can possess thermal conductive network, described reformation
Portion also can possess more than one transfer pin of heat.
In the present invention, combustion catalyst, reforming catalyst or carbon monoxide removal catalyst can comprise selected from gold, silver, ferrum,
More than one metal in cobalt, nickel, copper, manganese, aluminum, zinc, titanium, hafnium, rhodium, ruthenium, osmium, iridium, palladium, zirconium and lanthanum race metal or they
Oxide, specifically, described combustion catalyst can comprise more than one in platinum, rhodium, ruthenium, osmium, iridium, palladium, gold, silver and copper
Metal or their oxide, described in state reforming catalyst and can comprise selected from copper/cerium oxide/zirconia composite, copper/oxidation
More than any one 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 described raw material can comprise from the supply of described head tank to described heating
Adding hot charge and supplying the reformer feed pipe from the supply of described head tank to described reformer feed in raw material supply pipe.
Another aspect of the present invention is the hydrogen production process utilizing described hydrogen-manufacturing reactor, wherein, adds hot charge by including
Following steps and flow: a) add hot charge and be delivered to heat in feed line by adding hot charge supply pipe；B) by first
Compartment is delivered to combustion section from described heating feed line of stating, and occurs with the combustion catalyst being filled in described combustion section
React and carry out catalysis burning；And c) by combustion products discharge pipe, combustion products is expelled to after catalysis burning
The outside of reactor, reformer feed flows by comprising the following steps: 1) reformer feed is carried by reformer feed supply pipe
Gas phase is become mutually after to reformer feed phase transition tube；2) reformer feed of phase transformation passes through reformer feed discharge pipe and preheating pipe
And be delivered in the second compartment；3) reformer feed in supply extremely described second compartment passes through reforming section and with filling to reforming section
In reforming catalyst react；And 4) reaction is terminated after product be expelled to the outside of reactor.
Additionally, the present invention is described 3) after step, may additionally include reforming section end by carbon monoxide removal portion
Carbon monoxide removal catalyst layer also implements the step that selective carbon monoxide removal reacts.
In the present invention, described heating raw material or reformer feed can comprise water and 50 to 70 weight % of 30 to 50 weight %
Carbon compound, described 3) reforming catalyst can maintain the temperature range of 100 DEG C to 300 DEG C in step.Therefore, can be by pre-
Hot channel is arranged to be wound around downwards in the way of the peripheral contacts of the first housing.
The scheme more than recorded is not limited to described content, can easily replace including those skilled in the art
The all items changed.As an example, including the situation of the device made for the purpose of implementing identical technology otherwise.
(3) invention effect
According to the heat exchange type reactor for being produced hydrogen by carbon compound of the present invention, from outside successively with Heart-to-Heart
Structure is separated by and is provided with the first housing, the second housing and heating feed line, to being separated by by each housing and feed line
And the space produced fills combustion catalyst or reforming catalyst respectively, it is possible to the thermal capacitance by catalysis burning produces and easily transmit
In reforming catalyst, and freely regulate thermal gradient according to the filling situation of catalyst.
Particularly, the carbon monoxide removal portion that configures in one end of reforming section is had the advantage that such that it is able to drastically reduce
Carbonomonoxide concentration, and the heat transfer passing through to be produced by described carbon monoxide removal portion is to adjacent heating feed line
In and while being efficiently used system thermal, it is possible to use the catalysts in carbon monoxide removal portion steadily in the long term.
Additionally, inside is configured with raw material phase transformation portion, make the energy required for phase transformation by the heat of supply catalysis burning generation
Amount consumption minimizes, and can start rapidly reactor, therefore very economical under the state of cooling, and can reduce the big of reactor
Little make its compact conformation.
Additionally, carry out heating fuel by being arranged on the internal heater of heating feed line when initial launch
Gasification, and be together supplied in combustion catalyst with air, then in the case of liquid phase feed and combustion catalyst are discontiguous also
Can carry out stable combustion reaction, start once combustion reactor, combustion products is to being arranged on heating feed line
The reformer feed phase transition tube of upper end heats, and makes the liquid reformer feed gasification being supplied in reforming catalyst.Therefore, have
Following advantage: heating raw material and reformer feed can also be gasified the most rapidly and be supplied to by simple structure respectively
In individual catalyst layer.
In the case of the heat exchange type reactor of the present invention is connected with fuel cell, can use by advantage as above
Make the succedaneum of backup battery or lead battery, be widely used in not only in general energy system with hydrogen as fuel but also
It is positioned at and is difficult to supply in the terminating machine on out-of-the-way ground of electric power, repeater etc..
Accompanying drawing explanation
Fig. 1 to Fig. 6 is the figure of the section of the reactor illustrating one embodiment of the present of invention.
Fig. 7 is the figure of the section illustrating the internal reactor removing heating feed line.
Fig. 8 is the figure of the section illustrating the horizontal division board possessing heating feed line and reformer feed phase transition tube.
Fig. 9 and Figure 10 is the figure of the section illustrating heating feed line and reformer feed phase transition tube.
Figure 11 is the figure of the bottom illustrating the reformer feed phase transition tube being made up of coiled coil.
Figure 12 is the plane graph illustrating horizontal division board.
Description of reference numerals
1: reactor 2: the first housing
3: the second housings 4: horizontal division 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: add hot charge supply pipe
13: combustion products discharge pipe 14: reformer feed supply pipe
15: reformer feed discharge pipe 16: preheating pipe
17: the first compartment 18: the second compartments
19: thermal conductive network 20: transfer pin of heat
21: flange 22: bolster
23: guide punched-plate 24: reform and generate gas outlet pipe
25: heater
Detailed description of the invention
Below, utilize accompanying drawing and concrete example that the reactor by carbon compound manufacture hydrogen of the present invention is said in more detail
Bright.But, example or embodiment are only a reference for describing the present invention in detail in detail below, and the present invention is not limited to
This, can realize in many ways.
Additionally, without other define, the most all technical termses and scientific words have with the present invention belonging to technology neck
The implication that implication that some technical staff in the technical staff in territory are commonly understood by is identical.The use used in the explanation of the present invention
Language is only used for effectively describing specific embodiments, is not used for limiting the present invention.
Additionally, accompanying drawing introduced below is to fully pass on the thought of the present invention to provide to those skilled in the art
's.Therefore, the present invention is not limited to the following drawings, it is also possible to embody in other forms, in order to the clear and definite present invention's
Thought can enlarged representation accompanying drawing set forth below.Additionally, the most identical reference refers to identical composition
Component.
Additionally, about the singulative used in specification and claims, if the most particularly referred in article
Show, then this singulative can also include plural form.
About the reactor of the present invention, in FIG the raw material of the reformation in one end of reactor is supplied residing for pipe
End is referred to as " upper end ", and the other end relative with upper end is referred to as " lower end ".This is not only to reactor, and can also be to the first shell
Body, the second housing are suitable for above-mentioned identical top and bottom with feed line.
The term " concentric shafts " used in the present invention refers to when the direction observing response device flowing into described reactor from raw material
Time, connect the axle of the centre of figure that described first housing, the second housing and feed line are formed.Now, described figure
Central representation center of gravity, described first housing, the second housing and feed line can also be identical or different shapes.Additionally,
On the basis of the direction being perpendicular to described concentric shafts, with concentric shafts from described first housing, the second housing and feed line
Relative direction represents internal, and rightabout represents outside.
The term " raw material " used in the present invention is to be referred to as to comprise carbon compound and the liquid phase of water or gaseous substance, this raw material
Be stored in head tank, described raw material can comprise from described head tank to described add hot charge supply pipe supply " add pyrogen
Material " and supply, to described reformer feed, " reformer feed " that pipe supplies from described head tank.Hot charge and weight is added described in additionally,
Whole raw material can also have identical or different ratio of components, and the present invention is not limited to this.
Fig. 1 to Fig. 3 is the 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 the first housing of concentric structure, the second housing and a feed line, and described first housing, second
Housing and feed line are provided spaced.Additionally, inside is further equipped with reformer feed phase transition tube, thus at single reaction
The conveying of raw material, phase transformation, burning and reforming reaction can be carried out in device simultaneously.
Being described in more detail this, described reactor 1 is sealed by the first housing 2 and horizontal division board 4, described
The inside of reactor 1 possesses the second housing 3, heating feed line 10 and reformer feed phase transition tube 11.Additionally, isolate in level
It is provided with in the way of the most through horizontal division board 4 on plate and adds hot charge supply pipe 12, combustion products discharge pipe 13, reformation
Raw material supply pipe 14 and reformer feed discharge pipe 15, internally to supply reformer feed outside reactor or to add hot charge, or
After the reaction product is discharged to outside from inside reactor.
Described add hot charge supply pipe 12 for will heating feedstock transportation to heating feed line 10 in, described in add pyrogen
Material can carry out catalysis burning by the combustion catalyst 8 being laminated in described combustion section, and after catalysis burning, product passes through
Combustion products discharge pipe 13 is discharged to outside reactor.
Furthermore it is possible to supply independently by reformer feed with the hot charge that adds being supplied in described heating feed line 10
To pipe 14, reformer feed is supplied in reformer feed phase transition tube 11.Now, reformer feed phase transition tube 11 can be coil shape,
By the reformer feed of described reformer feed phase transition tube 11 can by reformer feed discharge pipe 15 be expelled to reactor outside and with
Preheating pipe 16 connects and is transported in the second compartment 18 of lower end.The reformer feed of conveying is fed in the second compartment 18
And while by being laminated to the reforming catalyst 6 within reforming section, be converted into the reformation gas rich in hydrogen and be discharged to reaction
Outside device.
In the present invention, the first housing 2 and the second housing 3 for metal material and have concentric shafts, described first housing 2 and the
Two housings 3 can be provided spaced and be formed reforming section 5.Additionally, reforming catalyst 6 can be filled with in reforming section.That is, such as figure
Shown in 2, the diameter of described first housing 2 is more than the diameter of the second housing 3, and described first housing 2 can have with by described second
The side of housing and the outside mode cut off completely around shape.Furthermore, it is possible to surround the second housing with reforming catalyst 6
The mode of a part in side is arranged.
Described reforming section 5 is the position that reformer feed is converted into containing hydroforming gas by reforming reaction, described in state reformation
A part in portion 5 can be filled with reforming catalyst 6, the upper end of described reforming section 5 can be formed discharge reform after former
The outlet of material.
Additionally, the lower end of the reactor 1 of the present invention lower end and described second housing can with the first housing separates and shape
Become the structure of the second compartment 18.Described second compartment plays the fuel reforming receiving gaseous state the stream being delivered to described reforming section
Effect.
The lower end of described reforming section 5 can possess guiding punched-plate 23, easily to fill reforming catalyst 6.Described guiding is rushed
Orifice plate 23 prevents described reforming catalyst 6 from falling to described second compartment 18 or in addition to scattered function, also having except having
Separate the function at interval between described reforming section and described second compartment 18.Additionally, described guiding punched-plate 23 can have net
Hole shape or hollow shape, so that described reformer feed easily flows into reforming section, but the present invention is not limited to this.
Preferably, described reforming catalyst 6 is filled from the lower end of reforming section, and point on the basis of described guiding punched-plate 23
Filling is separated with the upper end of described reforming section.Reforming catalyst does not the most limit with the standoff distance of reforming section, excellent
Selection of land, maintains standoff distance across guide with described reforming section identically with the lower end of described 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, described heating feed line 10 can be located at the inner side of described second housing 3, and has and the first shell
The concentric shafts that body 2 is identical with the second housing 3.Additionally, the second housing 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 described combustion section.
Described combustion section 7 makes heating material combusting be converted into heat energy and combustion products by catalyst combustion reaction
Position, the part in described combustion section 7 can fill with combustion catalyst, and by the first compartment 17 of lower end with add pyrogen
Material conveying tube 10 connects, and adds hot charge to receive.Additionally, in the upper end contacted with horizontal division board 4 can with run through described water
Flat division board and the combustion products discharge pipe 13 that arranges connect.
As shown in Figure 1 to Figure 3, described combustion catalyst 8 can make to fill out according to the temperature range of reforming section and thermograde
Fill position different with loading.As an example, as in figure 2 it is shown, can be straight by reducing the lower end of heating feed line 10
Footpath and gradually step up the loading of the combustion catalyst being filled into combustion section lower end, or as it is shown on figure 3, heating feed line
Lower end fill combustion catalyst further.This fails to reach required temperature and make for the temperature making up reforming section lower end
Reforming reaction is slow, and filling position and packed height freely can regulate according to the temperature of reforming section, and the present invention is not limited to
This.
Additionally, thermal conductive network 19 can be imported in addition to described combustion catalyst further in described combustion section 7, with more effectively
Pass through the heat that catalyst combustion reaction generates.Described thermal conductive network can be by by gold as higher in thermal conductivitys such as gold, silver, copper, aluminum
Belong to drawing fiber shape and weave and formed.This thermal conductive network has the advantage that can be by by generation after catalyst combustion reaction
Reaction product is while outside is discharged rapidly, by the heat transfer that fails to transmit in time to reforming section such that it is able to improve energy
Amount efficiency.
Described thermal conductive network 19 can be located at the part being not filled with combustion catalyst in described combustion section, it is preferable that permissible
The part residing for raw material phase transition tube being positioned in described combustion section in the way of surrounding raw material phase transition tube.
Described heating feed line 10 plays the heating feedstock transportation that is externally entering to the effect of combustion section, described
Heating feed line 10 can be formed by the material identical or different with described first housing 2 or the second housing 3.Additionally, can lead to
Cross the heating lower end of feed line and the lower end of described combustion section be separated by with the lower end of described second housing and formed first every
Room 17.
In the present invention, described reformer feed phase transition tube 11 is to lead in order to mutually described reformer feed is become liquid phase from gas phase
Entering, as shown in Fig. 1 to Fig. 3 and Fig. 9, described reformer feed phase transition tube 11 may be configured as adding pyrogen described in coil shape cladding
The lateral surface of material conveying tube 10.
The present invention can import heater 25 further, to be fed into the aqueous-phase reforming in described reformer feed phase transition tube 11
Raw material becomes gas phase mutually.The described position stating heater 25 may be disposed at the upper end of described heating feed line 10, i.e. described
Described heating feed line 10 and the described hot charge that adds in heating feed line 10 supply the position that pipe 12 connects.
Described heater 25 is wound around described heating feed line 10 with described reformer feed phase transition tube 11 with coil shape
Face be oppositely arranged such that it is able to effectively supply heat to described reformer feed phase transition tube 11.
In the present invention, as shown in Fig. 1 to Fig. 3 and Figure 12, described horizontal division board 4 is used for making described first housing 2, second
Housing 3 and heating feed line 10 are isolated from the outside, and add hot charge supply pipe 12, combustion products discharge pipe 13, weight
Whole raw material supply pipe 14 and reformer feed discharge pipe 15 run through described horizontal division board 4 along the direction parallel with described concentric shafts.
In the present invention, described horizontal division board 4 can be bonded by described first housing 2 and flange 21.Thus, it is not necessary to
Second housing 3 or heating feed line 10 bond respectively, it is possible to shorten built-up time.
In the present invention, described heating supply pipe 12 can be connected with described heating feed line 10, described combustion products
Discharge pipe 13 can be connected with described combustion section 7, described reformer feed supply pipe 14 and reformer feed discharge pipe 15 can respectively with institute
One end and the other end of stating reformer feed phase transition tube 11 connect.Owing to each pipe is connected with inside reactor such that it is able to guide
Add hot charge, reformer feed and reacted product make it effectively supply and discharge.
Additionally, the present invention will reform former to more effectively regulate the thermograde of described reforming section according to reformer feed
Material discharge pipe 15 is connected with preheating pipe 16, and described preheating pipe 16 can be (outer with the side of coil shape cladding reforming section 5
Wall).It guides heat exchange by likely producing cladding preheating pipe 16 on the outer wall of overheated position in reforming section, by
This can regulate the thermograde of reforming section.
In the present invention, if described preheating pipe 16 is capable of transmitting heat by being coated with the side of described reforming section 5
Purpose, then be not intended to position, the number of turn etc. being wound around, and described preheating pipe 16 can also be with the described direct phase of reforming section 5
It is wound around contiguously or is wound around at spaced intervals with described reforming section 5.
Additionally, as shown in Figure 8, in the reforming section of the reactor 1 of the present invention, transfer pin of heat 20 can be further equipped with, with by inciting somebody to action
Heat in reforming section Transmit evenly on the whole and improve the thermal efficiency further.The present invention does not limit the position of described transfer pin of heat
Put, shape, size, material etc., but preferably, may be configured as not hindering the type of flow of reformer feed to be connected by transfer pin of heat
Described first housing and the second housing, the material of described transfer pin of heat can use the material identical with the first housing and the second housing.
In the explanation of above-mentioned accompanying drawing, describe reforming section 5 be separated by space and shape by the first housing and the second housing
Becoming, and inside is filled with reforming catalyst 6, combustion section 7 is separated by space by the second housing and described heating feed line
And formed, and inside is filled with combustion catalyst 8, but described reforming section and combustion section can also transposition and arrange.That is, institute
State reforming section to be formed by the second housing and described being separated by space of heating feed line, and be positioned at inside reactor,
Described combustion section can be formed by the first housing and the second being separated by space of housing, and with the first housing as boundary and reactor
Outside connect.This can be according to the kind of the kind of the carbon compound included in raw material, reformation or combustion catalyst and carrying
When metal, burning, produced caloric value etc. regulate, and the present invention is not limited to this.
Fig. 4 to Fig. 6 is the sectional view of the hydrogen generation reactor of another embodiment of the present invention.Can save in the following description
The content slightly repeated with the content described in above-mentioned Fig. 1 to Fig. 3.
As shown in Figures 4 to 6, the reactor of the present invention is characterised by possessing carbon monoxide removal in reforming section downstream
Portion, described carbon monoxide removal portion is in being fed into the second compartment 18 at reformer feed and by being laminated to reforming section 5
After being converted into rich in the reformation gas of hydrogen while internal reforming catalyst 6, the carbon monoxide contained by removal.That is, its
Being characterised by, the reactor at aforesaid Fig. 1 to Fig. 3 farther includes carbon monoxide removal portion 9, described carbon monoxide removal
Portion 9 is removed rich in the gas of hydrogen by the rear end becoming the gas rich in hydrogen mutually while reformer feed is by reforming catalyst
Carbon monoxide.
Described carbon monoxide removal portion 9 possesses the catalyst that can remove carbon monoxide.The method removing carbon monoxide does not has
There is the biggest restriction, it is preferable that the selective methanation such as following reaction equation 2 can be implemented and react.
[reaction equation 2]
CO+3H2→CH4+H2O (heating, the methanation of carbon monoxide) (4)
CO2+4H2→CH4+2H2O (heating, carbon dioxide methanation) (5)
CO2+H2→CO+H2O (heat absorption, reverse water-gas-shift reaction) (6)
In above-mentioned reaction equation 2, (4) represent primary response, and it carries out methanation to carbon monoxide, and produce because of reaction and urge
Heating in agent layer.On the contrary, (5) and (6) represent side reaction, in the case of (6), can produce coal against the current by the endothermic reaction
Gas transformationreation.Thus, sizable reaction heat can be produced in carbon monoxide removal portion, make the temperature of catalyst layer improve, with
Shi Jinhang is as (5), (6) of side reaction, it is possible to reduce methanation conversion ratio and the selectance of carbon monoxide.
Especially, as shown in Figure 10 and Figure 11, the reformer feed phase transition tube 11 including the reactor in carbon monoxide removal portion 9 leads to
Crossing coiled coil i.e. primary winding (inner side) and secondary coil (outside) and connect, described reformer feed phase transition tube 11 has secondary
Coil is around the shape of the outer peripheral face of primary winding.Now, as the secondary line corral of a part of reformer feed phase transition tube 11
While heating feed line 10, surround the second shell in the position relative with carbon monoxide removal portion 9 across the second housing
The medial surface of body 3 so that adjoin with carbon monoxide removal portion 9, the heat that carbon monoxide removal portion 9 produces thus can be moved to weight
In whole raw material phase transition tube 11.That is, by the portion making described carbon monoxide removal portion 9 be positioned at and be formed with reformer feed phase transition tube 11
Point the similar position of height, make the latent heat by described reformer feed phase transition tube 11 and the exothermic reaction i.e. selectivity methane that produces
Change reaction and there is certain temperature range, thus thermal gradient regulation easiness in carbon monoxide removal portion and catalysts
Stability aspect is more favourable.This is able to maintain that certain temperature, to prevent the temperature of the catalysts because of carbon monoxide removal portion 9
Spend height and cause side reaction or catalyst damage.
Preferably, the catalyst layer in described carbon monoxide removal portion can have the temperature range of 200 to 300 DEG C.Meeting
In the case of above-mentioned scope, the methanation transformation efficiency of carbon monoxide is higher, it is possible to use carbon monoxide removal steadily in the long term
Catalysts in portion 9.
The reactor of reactor Fig. 1 to Fig. 3 as the aforementioned of Fig. 4 to Fig. 6 is the same, and the first housing 2 and the second housing 3 are gold
Belonging to material, and have concentric shafts, the first housing 2 and the second housing 3 are spaced from each other and form reforming section 5, in described reforming section 5
Upper end can be formed for the outlet that the raw material after reforming is discharged.But, in accompanying drawing, display is filled into the weight in described reforming section 5
Whole catalyst 6 is positioned at the position identical with reforming section 5, but is not limited to this, it is thus understood that reforming catalyst 6 is filled into reforming section
In 5.Additionally, the end being commonly referred to as described reforming section 5 is connected with carbon monoxide removal portion 9.
In the present invention, reforming catalyst 6 can comprise selected from gold, silver, ferrum, cobalt, nickel, copper, manganese, aluminum, zinc, titanium, hafnium, rhodium, ruthenium,
More than one metal in osmium, iridium, palladium, zirconium and lanthanum race metal or their oxide.Specifically, described reforming catalyst
6 can comprise selected from copper/cerium oxide/zirconia composite, copper/zinc oxide/alumina complex, copper/cerium oxide/alumina composite
The complex that any one in body and copper/zirconium oxide/alumina composite is above.
In more detail, can use copper: zinc: aluminum oxide with the weight ratio of 3 to 5:3 to 5:1 to 3 by Co deposited synthesis
Complex, but be not limited to this.
In the present invention, described combustion catalyst 8 can comprise selected from gold, silver, ferrum, cobalt, nickel, copper, manganese, aluminum, zinc, titanium, hafnium,
Rhodium, ruthenium, more than one the metal in osmium, iridium, palladium, zirconium and lanthanum race metal or their oxide, it is preferable that can be to be selected from
Such as platinum (platinum), rhodium (rhodium), ruthenium (ruthenium), osmium (osmium), iridium (iridium) and palladium
Etc. (palladium) platinum family element, gold, silver, copper or the group being made up of mixture more than two of which.
Additionally, described combustion catalyst 8 can be used in the carrier by carrying.Can be selected from oxygen as described carrier
Change aluminum, Alpha-alumina, zirconium dioxide (ZrO2), silicon dioxide (silica；SiO2) or by two of which thing mixed above structure
More than one in the group become.Additionally, do not limit the physical propertys such as the shape of particle of carrier, size, it is also possible to do not hindering
Freely regulate in the range of the object of the invention and use.
Additionally, described combustion catalyst 8 can regulate holding of metal or metal-oxide according to the thermograde of reforming section
Carrying capacity.That is, not can ensure that the situation of the temperature required for reaction by the reforming section temperature after measuring catalyst combustion reaction
Under, the metal of described combustion catalyst or the bearing capacity of metal-oxide can be improved, and can by the temperature in reforming section relatively
The combustion catalyst filling bearing capacity more in low segment set regulates the temperature met required for reforming reaction.
In the present invention, it is preferable that the internal carbon monoxide removal catalyst possessed in described carbon monoxide removal portion 9 can wrap
Containing in gold, silver, ferrum, cobalt, nickel, copper, manganese, aluminum, zinc, titanium, hafnium, rhodium, ruthenium, osmium, iridium, palladium, zirconium and lanthanum race metal one with
On metal or their oxide, but be not limited to this.
Below, based on fluid travel path, the present invention is described in more detail.
The described hot charge that adds flows by comprising the following steps:
A) pass through described in add hot charge supply pipe 12 be delivered in described heating feed line 10；
B) be delivered to described combustion section 7 from described heating feed line 10 by described first compartment 17, and with fill out
The combustion catalyst 8 being charged in described combustion section reacts, and carries out catalysis burning；And
C) after catalysis burning, by described combustion products discharge pipe 13, combustion products is discharged to reactor 1
Outside,
Described reformer feed flows by comprising the following steps:
1) reformer feed becomes gas phase after being delivered in reformer feed phase transition tube by reformer feed supply pipe mutually；
2) reformer feed of phase transformation is transported in the second compartment by reformer feed discharge pipe and preheating pipe；
3) reformer feed being supplied in described second compartment by reforming section and is urged with the reformation being filled in reforming section
Agent reacts；And
4) product after reaction being terminated is expelled to outside reactor.
Additionally, the present invention is above-mentioned 3) after step, reforming section end can be further included at and pass through carbon monoxide removal
The carbon monoxide removal catalyst layer in portion also implements the step of selective carbon monoxide removal reaction, and gone by carbon monoxide
Product after terminating except reaction is discharged to outside reactor.
Specifically, first, described reformer feed and described stating add hot charge and are stored in head tank (not shown), each
Raw material can also have identical or different composition.Described raw material can comprise the water of 30 to 50 weight % and 50 to 70 weight %
Carbon compound, about the content of described carbon compound, can be according to the composition of catalyst, the thermograde adjusting condition etc. of reforming section
Freely change ratio of components.
In the present invention, described carbon compound can comprise in this area as purposes such as organic synthesis material, solvent, detergents
The alcohol that uses, aldehyde, ketone, ester etc., described alcohol can enumerate the low order ethanol such as the ethanol in addition to methanol, butanol, in addition, also
The ketone of the aldehyde of formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde etc., acetone, butanone, pentanone etc. can be used.But, along with described carbon compound
Carbon amounts increase, also increase based on the impurity such as carbon deposition reformed, thus need accurately to adjust running temperature, therefore can also be excellent
Choosing uses methanol.
Described water uses usually used as solvent, thus can use pure water, and in order to save energy and improve reaction
Carry out speed, it is also possible to through warm.In the present invention, such as a) and b) step, first, described heating fuel is by described
Add hot charge supply pipe 12 to be delivered in described heating feed line 10, and be injected into the inside of reactor 1, adding after injection
Hot charge can be delivered in described combustion section 7 via heating feed line the 10, first compartment 17.That is, hot charge is added when described
Enter from upper end to lower end when heating feed line 10, when via the first compartment 17 and by described combustion section 7, can
Carry out to upper end from combustion section lower end.
Described catalysis burning is for carrying out adsorbing, move, react and producing catalyst surface layer is compound by heating fuel
Oxidation reaction, have and also be able to, because of relatively low active-energy, the advantage stably carrying out combustion reaction at a lower temperature.
Additionally, due to efficiency of combustion is higher, after reaction, product can be analyzed to nontoxic, tasteless carbon dioxide and oxygen, therefore without entering
The after-treatment of row waste water process etc., it is possible to the transconversion into heat speed of suppression combustion catalyst increases.
Heating fuel after reaction terminates is converted into carbon dioxide and water, and as above-mentioned c) step, by burning
Product discharge pipe 13 is to the outside discharge of reactor.
In the present invention, described reformer feed may travel to lower step: first, and 1) defeated by described reformer feed supply pipe 14
Deliver to described raw material phase transition tube 11, then, 2) described reformer feed is become gas phase mutually.
In the present invention, described reformer feed can supply with liquid phase, but can also be with according to the structure of technique and reactor
Gas phase supplies.In more detail, 1. carry out heating with heater 25 after supplying with liquid phase and carry out phase transformation at inside reactor,
Or before being injected into reactor 1,2. carry out phase transformation in advance, it is then supplied in reactor.Or, although it is supplied to liquid phase
In reactor but it also may the most first will add hot charge and supply to reactor, and be burnt by catalysis and receive heat, with in reaction
Phase transformation is carried out inside device.
Preferably, in the case of inside reactor carries out initial catalyst combustion reaction, stop heater 25 operation with
Save energy.This is because, as it has been described above, by described catalyst combustion reaction to reactor sustainable supply heat, thus described liquid
Phase reforming catalyst while raw material image converter tube 11 by spontaneous vaporization.
After reformer feed after phase transformation is expelled to reactor outside by described reformer feed discharge pipe 15, via preheating
Pipeline 16 moves in the second compartment 18.Now, as it has been described above, reformation can be wound around by described preheating pipe 16 with coil shape
The outside in portion (5) regulates the thermograde of reforming section.
Move to the reformer feed in the second compartment to be flowed in reforming section 5 via guiding punched-plate 23, and on carrying out
State 4) step.In described reforming section, by reforming catalyst 6, reformer feed can be converted into hydrogen, carbon dioxide, an oxygen
Change carbon and methane etc..
The reaction of reformer feed and reforming catalyst 6 is carried out by following reaction equation 1, and (2) of reaction equation 1 are the direct of methanol
Decomposition reaction, it is possible at high temperature local produces this decomposition reaction.
[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)
Above-mentioned 4) in step, the temperature being laminated to the reforming catalyst in reforming section 5 can be 100 DEG C to 300 DEG C.?
In the case of temperature is less than 100 DEG C, it is impossible to fully obtain the energy required for reforming reaction, thus carbon monoxide is converted into hydrogen
Conversion ratio be greatly reduced, in the case of more than 300 DEG C, owing to the carbon monoxide content in product increases, thus be difficult to
Remove carbon monoxide, and it is possible to drastically produce the thermal denaturation of reforming catalyst.
Carry out the product after reforming reaction to remove before being expelled to outside by generation gas outlet pipe 24 of reforming
It is supplied in fuel cell after carbon monoxide.Now, it is preferable that remove the oxygen generated in gas of reforming after carbon monoxide
Change concentration of carbon at below 10ppm.
Specifically, the method being used for removing carbon monoxide contained in described product can make with the following method: utilizes
Produce the reaction of selectivity Oxidation of Carbon Monoxide or the selectivity the methanation of carbon monoxide of the 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, carries out, with carbon monoxide, the oxygen that reacts to provide and supplies air, and by reformation gas
With the uniformly mixing of 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 safeguard.
It is thus preferable that can further include carbon monoxide removal catalyst in carbon monoxide removal portion, enabling real
Execute the selectivity the methanation of carbon monoxide reaction shown in reaction equation 4.But, the present invention is not limited to described selectivity carbon monoxide
Methanation reaction.
[reaction equation 4]
CO+3H2→CH4+H2O
Below, by embodiment, the present invention will be described in more detail.But, following example are only used for describing in detail
The example of the present invention, the present invention is not limited to this.
Embodiment 1
Reforming section is filled with the copper that the pallet shape with average diameter as 1.5mm as reforming catalyst is fabricated by
(Cu) constituent catalysts, is filled with platinum (Pt) catalyst being fabricated by with ceramic honeycomb (honeycomb) shape in combustion section.
Preheating pipe uses 1/8 inch pipe, and according to height at equal intervals the outside of reforming section is wound in coiled type, so that gasification
The heat further preheating that supplied by outer wall reforming section of reformer feed.
That raw material employs the methanol by mixing 60 weight % on the basis of quality and 40 weight % distilled water and make
Liquid fuel.Additionally, heating raw material uses identical liquid fuel with reformation raw material.As reformer feed, with 7.8g/
Min supplies described liquid fuel.Add hot charge to supply with the flow of 2.9g/min, in order to burn, withFlow velocity with
Time supply air, thus the maximum temperature regulating reforming section catalyst layer is maintained at less than 280 DEG C.Now, gas chromatograph is used
Analyze the composition of the product after reformation, and record in Table 1.Consisting of in bracket calculates at reaction temperature 250 DEG C
The value of equilibrium composition.The methanol conversion calculated by carbon amounts conservation formula reaches 96%, and the production hydrogen flowing quantity of calculating is
0.52Nm3/h。
[table 1]
Embodiment 2
Reforming section is filled with the copper that the pallet shape with average diameter as 1.5mm as reforming catalyst is fabricated by
(Cu) constituent catalysts comes, and is filled with platinum (Pt) catalysis being fabricated by with ceramic honeycomb (honeycomb) shape in combustion section
Agent.Preheating pipe uses 1/8 inch pipe, and according to height at equal intervals the outside of reforming section is wound in coiled type, so that
The heat preheating further that the reformer feed of gasification is supplied by outer wall reforming section.Additionally, the carbon monoxide at reforming section end goes
Except portion is filled with the catalyst of ruthenium (Ru) composition that the pallet shape with average diameter as 1.5mm is fabricated by.
Raw material employs the methanol by mixing 60 weight % on the basis of quality and the distilled water of 40 weight % and makes
Liquid fuel.Additionally, heating raw material uses identical liquid fuel with reformation raw material.As reformer feed, with 7.8g/
Min supplies described liquid fuel.Add hot charge to supply with the flow of 2.9g/min, in order to burn, withFlow velocity with
Time supply air, thus the maximum temperature regulating reforming section catalyst layer is maintained at less than 280 DEG C.Now, gas chromatograph is used
Analyze the composition of the product reformed and record in table 2.The content of carbon monoxide is below 10ppm, based on carbon amounts conservation formula
The methanol conversion calculated reaches more than 95%, 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 can comprise multiple change and change and equivalent
Thing, and can be by above-described embodiment is suitably deformed.Therefore, above-mentioned contents does not limit based on claims
The scope of the present invention that determines of restriction.
Claims (25)
1. a reactor, including: reforming section, the raw material comprising carbon compound and water by reformation generates hydrogeneous reformation
Gas；And combustion section, by the described raw material of burning to reforming section supply heat, wherein,
It is disposed with heating feed line, the first housing and the second housing with concentric structure from interior,
Described reforming section is formed by the space that is separated by of the first housing and the second housing, and described combustion section is by the second housing and adds pyrogen
The space that is separated by of material conveying tube is formed,
The inside of described combustion section includes the reformer feed phase transition tube heating raw material.
Reactor the most according to claim 1, wherein,
Described reactor includes: reforming section, being separated by space of described first housing and described second housing is filled with reformation and urges
Agent；And combustion section, described second housing and being separated by space of described heating feed line are filled with combustion catalyst.
Reactor the most according to claim 1, wherein,
One end of described reforming section also includes carbon monoxide removal portion.
Reactor the most according to claim 3, it is characterised in that
It is provided with in the second housing at and adjoining position relative with described carbon monoxide removal portion across the second housing
The reformer feed phase transition tube of side.
Reactor the most according to claim 3, wherein,
Described reactor includes the carbon monoxide removal portion being filled with carbon monoxide removal catalyst at the end of reforming section.
Reactor the most according to claim 1, wherein,
Heater or combustion catalyst is also included in the inside of described heating feed line.
Reactor the most according to claim 1, wherein,
The lower end of the lower end of described heating feed line and described second housing is spaced from each other and forms the first compartment, and described the
The lower end of two housings is spaced from each other with the lower end of described first housing and forms the second compartment.
Reactor the most according to claim 1, wherein,
It is also equipped with described heating feed line, described first housing and described general in the upper end of described heating feed line
The horizontal division board that second housing is isolated from the outside.
Reactor the most according to claim 8, wherein,
Described horizontal division board is set to add hot charge supply pipe, combustion products discharge pipe, reformer feed supply pipe and reform
Raw material discharge pipe runs through described horizontal division board.
Reactor the most according to claim 9, wherein,
The described hot charge supply pipe that adds is connected with heating feed line, and described combustion products discharge pipe is connected with combustion section,
Described reformer feed supply pipe and reformer feed discharge pipe are connected with one end and the other end of reformer feed phase transition tube respectively.
11. reactors according to claim 10, wherein,
Described reformer feed discharge pipe is connected with described second compartment.
12. reactors according to claim 9, wherein,
Described reformer feed discharge pipe is connected with preheating pipe, and described preheating pipe is coated with the outside of the first housing with coil shape
Face.
13. reactors according to claim 1, wherein,
The part being filled with reforming catalyst in the lateral surface of described first housing is also equipped with more than one temperature sensor.
14. reactors according to claim 1, wherein,
The space being not filled by combustion catalyst in described combustion section is also equipped with thermal conductive network.
15. reactors according to claim 1, wherein,
Described reforming section is also equipped with more than one transfer pin of heat.
16. reactors according to claim 2, wherein,
Described combustion catalyst or reforming catalyst comprise selected from gold, silver, ferrum, cobalt, nickel, copper, manganese, aluminum, zinc, titanium, hafnium, rhodium, ruthenium,
More than one metal in osmium, iridium, palladium, zirconium and lanthanum race metal or their oxide.
17. reactors according to claim 16, wherein,
Described combustion catalyst comprise more than one the metal in platinum, rhodium, ruthenium, osmium, iridium, palladium, gold, silver and copper or they
Oxide.
18. reactors according to claim 16, wherein,
Described reforming catalyst comprises selected from copper/cerium oxide/zirconia composite, copper/zinc oxide/alumina complex, copper/oxygen
Change the complex that any one in cerium/alumina composite and copper/zirconium oxide/alumina composite is above.
19. reactors according to claim 5, wherein,
Described carbon monoxide removal catalyst comprise selected from gold, silver, ferrum, cobalt, nickel, copper, manganese, aluminum, zinc, titanium, hafnium, rhodium, ruthenium, osmium,
More than one metal in iridium, palladium, zirconium and lanthanum race metal or their oxide.
20. according to the reactor described in any one in claim 1 to 19, wherein,
Described raw material is stored in head tank, and described raw material comprises and adds hot charge supply pipe to described from the supply of described head tank
Add hot charge and from described head tank supply to described reformer feed supply pipe reformer feed.
21. 1 kinds of raw material reforming methods utilizing hydrogen-manufacturing reactor, it is the hydrogen manufacturing utilizing the reactor described in claim 20
Method, wherein,
Add hot charge to flow by comprising the following steps:
A) add hot charge and be delivered to heat in feed line by adding hot charge supply pipe；
B) be delivered to combustion section from described heating feed line by the first compartment, and be filled in described combustion section
Combustion catalyst reacts and carries out catalysis burning；And
C) by combustion products discharge pipe, combustion products is expelled to outside reactor after catalysis burning,
Reformer feed flows by comprising the following steps:
1) reformer feed becomes gas phase after being delivered in reformer feed phase transition tube by reformer feed supply pipe mutually；
2) reformer feed of phase transformation is delivered in the second compartment by reformer feed discharge pipe and preheating pipe；
3) supply to the reformer feed in described second compartment by reforming section and with the reforming catalyst being filled in reforming section
React；And
4) product after reaction being terminated is expelled to outside reactor.
The 22. raw material reforming methods utilizing hydrogen-manufacturing reactor according to claim 21, wherein,
Described heating fuel or fuel reforming comprise water and the carbon compound of 50 to 70 weight % of 30 to 50 weight %.
The 23. raw material reforming methods utilizing hydrogen-manufacturing reactor according to claim 21, wherein,
Described 3) in step, described reforming catalyst has the temperature range of 100 DEG C to 300 DEG C.
The 24. raw material reforming methods utilizing hydrogen-manufacturing reactor according to claim 21, wherein,
Described 3) after step, it is additionally included in the reforming section end carbon monoxide removal catalyst by carbon monoxide removal portion
Layer also implements the selective step removing reaction.
The 25. raw material reforming methods utilizing hydrogen-manufacturing reactor according to claim 24, wherein,
Described 4) in step, described in state carbon monoxide removal catalyst layer there is the temperature range of 200 DEG C to 300 DEG C.
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| KR10-2015-0090915 | 2015-06-26 | ||
| KR1020150090915A KR101817569B1 (en) | 2015-06-26 | 2015-06-26 | A heat-exchange reactor producing hydrogen from carbon compound |
| KR1020160070831A KR101830954B1 (en) | 2016-06-08 | 2016-06-08 | Hydrogen production system including unit for removal of carbon monoxide |
| KR10-2016-0070831 | 2016-06-08 |
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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 |
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