CN205933211U - Selective oxidation purifies CO's methanol reforming reactor - Google Patents
Selective oxidation purifies CO's methanol reforming reactor Download PDFInfo
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- CN205933211U CN205933211U CN201620939480.2U CN201620939480U CN205933211U CN 205933211 U CN205933211 U CN 205933211U CN 201620939480 U CN201620939480 U CN 201620939480U CN 205933211 U CN205933211 U CN 205933211U
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Abstract
The utility model relates to a selective oxidation purifies CO's methanol reforming reactor, with at least one CO purified reaction ware that is arranged in reducing the hydrogen -rich gas CO that the reforming reaction produced, this CO purified reaction ware has an input port and an output port at least including the reforming reaction room, and input port and the reformation synthetic gas output port of reforming reaction room are connected, and output port is used for the hydrogen -rich gas after the output purification, and the CO purified reaction ware is equipped with oxygen or purified reaction 0 at least, and there is the catalyst obturator that is used for purified reaction 1CO to react inside. Adopt selective oxidation to purify CO, can cross CO content among the hydrogen -rich gas that reduce the production of reforming reaction room effectively. Reforming reaction room and CO purified reaction ware adopt the integrated design, have further alleviateed weight and have made compact structure ization. The methanol reforming reactor main with proton exchange membrane fuel cell antithetical couplet usefulness, provide hydrogen for proton exchange membrane fuel cell.
Description
Technical field
The utility model is related to reforming hydrogen producing technology field, particularly a kind of preparing hydrogen by reforming methanol and purify reforming reaction
The reaction unit of CO in the hydrogen-rich gas obtaining.
Background technology
In numerous new forms of energy, Hydrogen Energy will become the 21 century optimal energy.Burning identical coal, gasoline and
In the case of hydrogen, the energy that hydrogen produces is most, and the product that it burns is water, does not have lime-ash and waste gas, will not pollute
Environment.
Proton Exchange Membrane Fuel Cells（PEMFC）Need pure hydrogen as fuel, but the transport of pure hydrogen, storage, loading technique
And facility can not meet decentralized power station, especially into the requirement of family's use, therefore by the storage of existing fossil fuel
Fortune additional facilities, mode and PEMFC using fuel reforming hydrogen manufacturing are used in combination the universal method becoming international.
Preparing hydrogen by reforming methanol is methyl alcohol with vapor at a temperature of 350 DEG C -409 DEG C, under the pressure condition of 1-5MPa, is urging
In the presence of agent, there is methanol decomposition reaction and the transformationreation of CO, generate H2And CO, this is a multicomponent, many reactions
Gas-solid phase reaction system.Reactional equation is as follows：
CH3OH→CO+H2（1）
H2O+CO→CO2+H2（2）
CH3OH+H2O→CO2+3H2（3）
The H that reforming reaction generates2And CO2, then through palladium membrane separator by H2And CO2Separate, obtain high-purity hydrogen.
Hydrogen-rich gas from reforming reactor comprises 45-75%H2、15-25%CO2, 0.5%-2%CO and a small amount of H2O and
N2.Because the electrode material of hydrogen fuel cell is Pt, CO not only can poison Pt electrode but also easily be adsorbed in catalyst surface, hinder
The catalysis oxidation of fuel.Substantial amounts of research shows that the CO of denier can be just battery performance degradation.
Thus, select a kind of method of good reduction CO concentration just to become the key difficulties of Proton Exchange Membrane Fuel Cells.
Content of the invention
The technical problems to be solved in the utility model is the methanol steam reforming device providing a kind of selective oxidation to purify CO,
At least to solve the problems, such as to reduce CO content in the hydrogen-rich gas that reforming reactor produces.
For solving above technical problem, the utility model provides a kind of selective oxidation to purify the methanol steam reforming of CO
Device, including reforming reaction room, also includes at least one and purifies instead for the CO reducing CO in the hydrogen-rich gas that reforming reaction produces
Answer device, at least one input port of this CO purification reactor and an output port, the weight of input port and reforming reaction room
It is integrated into gas output port to connect, output port is used for the hydrogen-rich gas after output purifies, and CO purification reactor is at least provided with one
Individual oxygen or air inlet duct, there is the catalyst obturator for selective oxidation CO reaction inside.
As preferred technical scheme, described catalyst obturator is Pt race noble metal catalyst, Au catalyst and copper
At least one in series catalysts.
As preferred technical scheme, along the input port of CO purification reactor to output port direction, arrange two or
Two or more oxygen or air inlet duct.
As preferred technical scheme, the selective oxidation that the utility model provides purifies the methanol steam reforming device bag of CO
Include combustion chamber, reforming reaction room and evaporimeter, described combustion chamber is used for methyl alcohol and produces heat, combustion chamber with combustion adjuvant burning
It is connected with fuel methanol input pipe and combustion adjuvant input pipe；Described evaporimeter is used for exchanging the heat of combustion chamber by material benzenemethanol
And water vapor, the input port of evaporimeter is connected with material benzenemethanol input pipe and raw material water inlet pipe, the output port of evaporimeter
It is connected with reforming reaction room；Described reforming reaction room is used for material benzenemethanol and carries out reforming reaction generation reformed syngas with water,
Material mixed gas input port and reformed syngas output port, material mixed gas input port and evaporation are had on reforming reaction room
The output port of device is connected.
Preferably, the methanol steam reforming device that the selective oxidation that the utility model provides purifies CO is included for accommodating combustion
Burn the housing of room, reforming reaction room and evaporimeter, combustion chamber and reforming reaction room are cavity cylinder, and combustion chamber is arranged on housing
Interior middle part, reforming reaction room is arranged on combustion chamber bottom, reforming reaction interior filling reforming reaction catalyst, and top of combustion chamber is even
Connect fuel methanol input pipe and combustion adjuvant input pipe, top of combustion chamber is also equipped with igniter；Evaporimeter adopts coil arrangement,
Evaporator plate is around in outside combustion chamber, the input port of evaporimeter be arranged on evaporimeter top and with material benzenemethanol input pipe and former
Material water inlet pipe is connected, and the output port of evaporimeter is arranged on base of evaporator and is connected with reforming reaction room；Reforming reaction room
On set material mixed gas input port and reformed syngas output port, the output end of material mixed gas input port and evaporimeter
Mouth connects.
As preferred technical scheme, described CO purification reactor is the annular hollow being arranged on above reforming reaction room
Cylinder, the input port of CO purification reactor and output port are separately positioned on CO purification reactor（Lower end and upper end, two
Or two or more oxygen or air inlet duct are distributed in CO purification reactor along short transverse.
In hydrogen-rich gas, CO content is higher, and about 0.5%-2% is it is necessary to control 20 × 10 through purification-6Hereinafter, Cai Nengman
The requirement to CO for the sufficient Proton Exchange Membrane Fuel Cells.At present, the method reducing CO content mainly has absorption, Pd membrane separation process, but
It is that adsorption method volume is big, and adsorption capacity is limited；Pd UF membrane cost is too high, and Pd film has hydrogen embrittlement problem simultaneously.Therefore,
The utility model uses removing CO by selective oxidation reaction, and this reaction is to introduce oxygen or air in hydrogenrich gas,
Selective oxidation CO, thus reaching the purpose of removing CO, equation is CO+1/2O2=CO2.The catalyst commonly used at present is mainly
Pt race noble metal catalyst, Au catalyst and Cu-series catalyst.Catalyst is harsher to the condition of temperature, and temperature range is very
Narrow it is desirable to precise control enters the amount of oxygen in reactor, and reactor will have good heat dispersion, Pt/Al2O3Catalysis
Agent can effectively in selective oxidation removal methanol recapitalization hydrogen source CO.
Methanol steam reforming device disclosed in the utility model, using removing CO by selective oxidation, overcomes absorption, Pd film divides
The problem existing from method, can cross CO content in the hydrogen-rich gas being effectively reduced the generation of reforming reaction room.Reforming reaction room and CO
Purification reactor adopts integrated design, further mitigates weight and makes compact conformation.Methyl alcohol weight described in the utility model
Whole reactor is main and Proton Exchange Membrane Fuel Cells is combined, and provides hydrogen for Proton Exchange Membrane Fuel Cells.
Additionally, the utility model is on startup, produces heat using industrial methanol burning, the temperature required for reforming reaction is provided
Degree, compared with conventional methanol reforming reactor, on the one hand, directly use liquid fuel to simplify structure, after on the other hand lighting i.e.
Required reaction temperature can be quickly heated up to, decrease starting time, working stability, highly reliable.
The utility model is particularly well-suited to may move, portable small fuel cell power-supply system.
Brief description
Accompanying drawing herein is used for providing further illustrating to of the present utility model, constitutes the part of the application, this practicality
New schematic description and description is used for explaining the utility model, does not constitute to improper restriction of the present utility model.
Fig. 1 is connection diagram of the present utility model.
Fig. 2 is structural representation of the present utility model.
In figure, 1- reforming reaction room, 2- combustion chamber, 3- evaporimeter, 4- housing, 5- fuel methanol input pipe, 6- combustion adjuvant
Input pipe, 7- material benzenemethanol input pipe, 8- raw material water inlet pipe, 9- flange, 10-CO purification reactor, 11- oxygen or air are defeated
Enter pipe, 12- catalyst obturator, 13- Proton Exchange Membrane Fuel Cells, 14- peristaltic pump.
Specific embodiment
In order that those skilled in the art are better understood from the utility model, below in conjunction with refer to the attached drawing and in conjunction with the embodiments
Clear further, complete explanation is made to the utility model.It should be noted that in the case of not conflicting, in the application
Feature in embodiment and embodiment can be mutually combined.
Selective oxidation shown in Fig. 1 purifies the methanol steam reforming device of CO, including reforming reaction room 1, also includes at least
One CO purification reactor 10 being used for CO in the hydrogen-rich gas reduce reforming reaction generation, this CO purification reactor 10 is at least
One input port and an output port, input port is connected with the reformed syngas output port of reforming reaction room 1, defeated
Exit port be used for output purify after hydrogen-rich gas, CO purification reactor 10 at least provided with an oxygen or air inlet duct 11,
There is the catalyst obturator 12 for selective oxidation CO reaction inside.
Preferably, above-mentioned catalyst obturator 12 is in Pt race noble metal catalyst, Au catalyst and Cu-series catalyst
At least one.
Pass through reforming reaction room output port from reforming reaction room hydrogen-rich gas out and enter CO purification reactor.In CO
In purification reactor, the CO content in hydrogen-rich product stream is reduced to and can be used for Proton Exchange Membrane Fuel Cells 13.
As shown in figure 1, as preferred embodiment, methanol steam reforming device that the utility model provides include combustion chamber 2,
Reforming reaction room 1 and evaporimeter 3, described combustion chamber 2 is used for methyl alcohol and produces heat, combustion chamber 2 and combustion with combustion adjuvant burning
Material methyl alcohol input pipe 5 is connected with combustion adjuvant input pipe 6；Described evaporimeter 3 is used for exchanging the heat of combustion chamber 2 by material benzenemethanol
And water vapor, the input port of evaporimeter 3 is connected with material benzenemethanol input pipe 7 and raw material water inlet pipe 8, the output of evaporimeter 3
Port is connected with reforming reaction room 1；Described reforming reaction room 1 is used for material benzenemethanol and carries out reforming reaction generation reformation conjunction with water
Become gas, on reforming reaction room, 1 has material mixed gas input port and reformed syngas output port, material mixed gas input port
It is connected with the output port of evaporimeter.
As shown in Fig. 2 as another preferred embodiment, methanol steam reforming device is included for housing combustion chamber 2, reforming
The housing 4 of reative cell 1 and evaporimeter 3, combustion chamber 2 and reforming reaction room 1 are cavity cylinder, preferably cavity cylinder, combustion
Burn room 2 and be arranged on middle part in housing 4, reforming reaction room 1 is arranged on combustion chamber 2 bottom, filling reforming reaction in reforming reaction room 1
Catalyst, combustion chamber 1 top connects fuel methanol input pipe 5 and combustion adjuvant input pipe 6, and combustion chamber 2 top is also equipped with lighting a fire
Device（In figure is not shown）, above-mentioned fuel methanol input pipe 5, combustion adjuvant input pipe 6 and igniter are each attached to flange 9
On, this flange 9 is connected with combustion chamber 1 top bolt.Evaporimeter 3 adopts coil arrangement, and evaporimeter 3 coils outside combustion chamber,
The input port of evaporimeter 3 is arranged on evaporimeter 3 top and is connected with material benzenemethanol input pipe 7 and raw material water inlet pipe 8, evaporation
The output port of device 3 is arranged on evaporimeter 3 bottom and is connected with reforming reaction room.Material mixed gas are set defeated on reforming reaction room 1
Inbound port and reformed syngas output port, material mixed gas input port is connected with the output port of evaporimeter 3.
As another kind of preferred embodiment, along the input port of CO purification reactor 10 to output port direction, arrange
Two or more oxygen or air inlet duct 11.On architecture basics, oxygen mode can be entered using multistage, due to purifying along CO
The input port of reactor to output port, successively decrease, and enters oxygen using multistage by the concentration of CO, can be independent to every section of air inflow
It is configured, be conducive to the CO of different parts and oxygen or air to be sufficiently mixed and react.As shown in Fig. 2 CO purification reactor
10 is the annular hollow cylinder being arranged on reforming reaction room 1 top, and the input port of CO purification reactor 10 and output port divide
It is not arranged on lower end and the upper end of CO purification reactor 10, two or more oxygen or air inlet duct 11 are along short transverse
It is distributed in CO purification reactor 10.Fig. 2 shows three sections of oxygen or air inlet duct 11, respectively near input port, in
Pore, the gas in oxygen or air inlet duct 11 are distributed with portion and the position of output port, oxygen or air inlet duct 11
Can uniformly spread to CO purification reactor 10, corresponding to the CO concentration around each section, different gas flow rates can be set, close
Gas tolerance in the oxygen of input port or air inlet duct 11 is larger, and the tolerance at middle part is taken second place, near the gas of output port
Amount is less.
Combustion chamber 2 provides heat for reforming reaction, and fuel is methyl alcohol, and combustion adjuvant is at least one in air and oxygen,
Combustion product is CO2And H2O, releases heat in combustion process, has nozzle, igniter and air distribution pipe in combustion chamber 2.Should
Reaction can be burnt rapidly and be produced heat, so that combustion chamber 2 and reforming reaction room 1 are brought rapidly up required temperature.Fuel first
Alcohol input pipe 5 and combustion adjuvant input pipe 6 are respectively used to input fuel methanol and combustion adjuvant into combustion chamber 2.Evaporimeter 3 is raw material
The vaporization place of first alcohol and water, material benzenemethanol and water pass through material benzenemethanol input pipe 7 and raw material water inlet pipe 8 respectively from evaporimeter
3 input port input evaporimeter 3, the mixed gas after vaporization export to reforming reaction room 1 from the output port of evaporimeter 3.
In reforming reaction room 1, the reaction of first alcohol and water generates reformed syngas, and methanol reforming catalyst mainly has nickel catalyst, platinum palladium to urge
Agent and Cu-series catalyst, wherein, the reaction temperature of Cu-series catalyst at 230 DEG C -270 DEG C, its catalysis activity, reaction selectivity
Good.
When methanol steam reforming device starts, fuel methanol passes through peristaltic pump 14, fuel methanol input pipe 5 enters combustion chamber 2
The nozzle at top, fuel methanol is mixed with combustion adjuvant air or oxygen, is sprayed onto in combustion chamber 2, rapid in the presence of igniter
Burning produces heat.Rapidly to evaporimeter 3 and the conduction of reforming reaction room 1 inner chamber, material benzenemethanol and water exist the heat that combustion chamber 2 produces
In evaporimeter 3, vaporization forms mixed raw material gas, and the mixed gas of heat enter reforming reaction room 1 and occur in the presence of catalyst
Reforming reaction produces hydrogen-rich gas.Hydrogen-rich gas reduces CO content further across CO purification reactor, is then sent to proton
Exchange film fuel battery 13 produces electric power, and the converted product of use completely can not sent combustion chamber back to and be provided heat for reaction.
The scope that the utility model claims is not limited to above specific embodiment, for those skilled in the art
Speech, the utility model can have various deformation and a change, all made within design of the present utility model with principle any repair
Change, improve and equivalent all should be included within protection domain of the present utility model.
Claims (6)
1. a kind of selective oxidation purifies the methanol steam reforming device of CO, including reforming reaction room（1）It is characterised in that：Also wrap
Include at least one for the CO purification reactor reducing CO in the hydrogen-rich gas that reforming reaction produces（10）, this CO purification reactor
（10）At least one input port and an output port, input port and reforming reaction room（1）Reformed syngas output
Port connects, and output port is used for the hydrogen-rich gas after output purifies, CO purification reactor（10）At least provided with an oxygen or
Air inlet duct（11）, there is the catalyst obturator for selective oxidation CO reaction inside（12）.
2. selective oxidation according to claim 1 purify CO methanol steam reforming device it is characterised in that：Described
Catalyst obturator（12）For at least one in Pt race noble metal catalyst, Au catalyst and Cu-series catalyst.
3. selective oxidation according to claim 2 purify CO methanol steam reforming device it is characterised in that：Purify along CO
Reactor（10）Input port to output port direction, two or more oxygen or air inlet duct are set（11）.
4. selective oxidation according to claim 1 and 2 purify CO methanol steam reforming device it is characterised in that：Also wrap
Include combustion chamber（2）And evaporimeter（3）, described combustion chamber（2）Produce heat, combustion chamber for methyl alcohol with combustion adjuvant burning（2）
With fuel methanol input pipe（5）With combustion adjuvant input pipe（6）It is connected；Described evaporimeter（3）For exchanging combustion chamber（2）Heat
Measure material benzenemethanol and water vapor, evaporimeter（3）Input port and material benzenemethanol input pipe（7）With raw material water inlet pipe（8）
It is connected, evaporimeter（3）Output port and reforming reaction room（1）It is connected；Described reforming reaction room（1）For material benzenemethanol with
Water carries out reforming reaction and produces reformed syngas, reforming reaction room（1）On have material mixed gas input port and reformed syngas
Output port, material mixed gas input port and evaporimeter（3）Output port be connected.
5. selective oxidation according to claim 4 purify CO methanol steam reforming device it is characterised in that：Including for
Accommodating combustion chamber（2）, reforming reaction room（1）And evaporimeter（3）Housing, combustion chamber（2）With reforming reaction room（1）It is cavity
Cylinder, combustion chamber（2）It is arranged on housing（4）Interior middle part, reforming reaction room（1）It is arranged on combustion chamber（2）Bottom, reforming reaction room
（1）Interior filling reforming reaction catalyst, combustion chamber（2）Top connects fuel methanol input pipe（5）With combustion adjuvant input pipe（6）,
Combustion chamber（2）Top is also equipped with igniter；Evaporimeter（3）Using coil arrangement, evaporimeter（3）Coil outdoor in burning
Side, evaporimeter（3）Input port be arranged on evaporimeter（3）Top and with material benzenemethanol input pipe（7）With raw material water inlet pipe
（8）It is connected, evaporimeter（3）Output port be arranged on evaporimeter（3）Bottom and with reforming reaction room（1）It is connected；Reforming reaction
Room（1）On set material mixed gas input port and reformed syngas output port, material mixed gas input port and evaporimeter（3）
Output port connect.
6. selective oxidation according to claim 5 purify CO methanol steam reforming device it is characterised in that：Described CO
Purification reactor（10）For being arranged on reforming reaction room（1）The annular hollow cylinder of top, CO purification reactor（10）Input
Port and output port are separately positioned on CO purification reactor（10）Lower end and upper end, two or more oxygen or air
Input pipe（11）It is distributed in CO purification reactor along short transverse（10）Interior.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201620939480.2U CN205933211U (en) | 2016-08-25 | 2016-08-25 | Selective oxidation purifies CO's methanol reforming reactor |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201620939480.2U CN205933211U (en) | 2016-08-25 | 2016-08-25 | Selective oxidation purifies CO's methanol reforming reactor |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114249298A (en) * | 2022-02-24 | 2022-03-29 | 清华大学 | Methanol reformer and fuel cell |
-
2016
- 2016-08-25 CN CN201620939480.2U patent/CN205933211U/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114249298A (en) * | 2022-02-24 | 2022-03-29 | 清华大学 | Methanol reformer and fuel cell |
| CN114249298B (en) * | 2022-02-24 | 2022-06-21 | 清华大学 | Methanol reformer and fuel cell |
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