CN105776133B - Methane reformer system - Google Patents

Methane reformer system Download PDF

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Publication number
CN105776133B
CN105776133B CN201610112216.6A CN201610112216A CN105776133B CN 105776133 B CN105776133 B CN 105776133B CN 201610112216 A CN201610112216 A CN 201610112216A CN 105776133 B CN105776133 B CN 105776133B
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hydrogen
carbon dioxide
methane
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CN201610112216.6A
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CN105776133A (en
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郝勇
王宏圣
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中国科学院工程热物理研究所
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/133Renewable energy sources, e.g. sunlight
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals

Abstract

The invention provides a kind of methane reformer system.In the methane reformer system, methane and vapor pipeline flow through hydrogen separation device and carbon dioxide separation device and form circulation successively, methane wet reformate hydrogen and carbon dioxide are alternately separated, promote methane reforming reaction to balance mobile to forward direction, methane conversion is significantly lifted compared to single reaction conversion ratio when not circulating.In addition, increasing heat exchanger between hydrogen separation device and carbon dioxide separation device, recovery, can also the lifting of the amount of enabling the system to utilization rate because thermal losses of the hydrogen separation device caused by with the operation temperature difference of carbon dioxide separation device.

Description

Methane reformer system
Technical field
The present invention relates to new energy (regenerative resource) technical field, more particularly to a kind of methane reformer system.
Background technology
Hydrogen is a kind of very high clean energy resource of energy density, how high efficiency, low cost hydrogen making be that current various countries are ground The focus studied carefully.Traditional industrial hydrogen production mode is mainly by methane and steam reforming at present, reaction temperature more than 700 DEG C, Higher not only is required to the heat resistance of equipment, and methane reforming reaction needs to absorb amount of heat, these energy essentially from Burnt in fossil energy, energy expenditure is larger, and the energy utilization efficiency of methane reformer system is relatively low.
The content of the invention
(1) technical problems to be solved
The invention provides a kind of methane reformer system, to reduce methane reforming hydrogen making cost, improves methane conversion Rate.
(2) technical scheme
Methane reformer system of the present invention includes:Hydrogen separation device, its medial compartment are divided into first kind region and the second class Region, wherein, the hydrogen dividing potential drop in the second class region when the hydrogen dividing potential drop in first kind region is less than methane and steam reforming reaction;Dioxy Change carbon separator, its medial compartment is divided into the 3rd class region and the 4th class region, wherein, the carbon dioxide point in the 3rd class region The carbon dioxide partial pressure in the 4th class region when pressure is less than methane and steam reforming reaction, also, the import in the 4th class region The outlet in the second class region is connected to, the outlet in the 4th class region is connected to the import in the second class region.Wherein, methane and water steam Gas enters the second class region of hydrogen separation device, and methane reforming reaction occurs, and the hydrogen of generation enters first kind region, reforms Reaction balance is mobile to forward direction, and unreacting gas continue to react;Then, reacted gas enters titanium dioxide in the second class region 4th class region of carbon separator, remaining carbon dioxide enters the 3rd class region after separating hydrogen;Then, the 4th class region The second class region that interior residual gas reenters hydrogen separation device carries out methane reforming reaction.
(3) beneficial effect
It can be seen from the above technical proposal that methane reformer system of the present invention has the advantages that:
(1) methane and vapor pipeline flow through hydrogen separation device and carbon dioxide separation device and form circulation successively, Methane wet reformate hydrogen and carbon dioxide are alternately separated, and are promoted methane reforming reaction to balance mobile to forward direction, are made methane Conversion ratio is significantly lifted compared to single reaction conversion ratio;
(2) heat exchanger is increased between hydrogen separation device and carbon dioxide separation device, recovery is because hydrogen separation device Thermal losses caused by different with the operation temperature of carbon dioxide separation device, the lifting of the amount of enabling the system to utilization rate;
(3) hydrogen separation device and carbon dioxide separation device can use membrane material to separate, in membrane material material separating device More membrane material pipe materials can be placed using barrel forms, in chamber outer wall 5, is advantageous to increase membrane material specific surface area, improves Space availability ratio;
(4) system can be combined with discarded energy such as new energy and industrial waste heat such as solar energy or nuclear energy, wiper ring Protect.
Brief description of the drawings
Fig. 1 is the structural representation according to first embodiment of the invention methane reformer system;
Fig. 2 is membrane material material separating device schematic diagram in methane reformer system shown in Fig. 1;
Fig. 3 is that methane reformer system shown in Fig. 1 circulates methane in hydrogen separation device and titanium dioxide for first 4 at 400 DEG C Remaining proportion in carbon separator;
Fig. 4 is that methane reformer system shown in Fig. 1 circulates vapor in hydrogen separation device and dioxy for first 4 at 400 DEG C Change the remaining proportion in carbon separator.
【Main element of the present invention meets explanation】
1- hydrogen separation devices;2- heat exchangers;
3- carbon dioxide separation devices;4- solar-energy light collectors;
5- chamber outer walls;6- membrane material pipe materials;
7- reaction gas inlets;8- products separated region.
Embodiment
The present invention utilizes catalyst methane reforming, and alternately separation product, can by way of unreacting gas circulation Reaction temperature is set to significantly reduce to less than 400 DEG C, if disregarding methane oxidizing archaea, methane conversion is up to 100%.
For the object, technical solutions and advantages of the present invention are more clearly understood, below in conjunction with specific embodiment, and reference Accompanying drawing, the present invention is described in more detail.
First, first embodiment
In one exemplary embodiment of the present invention, there is provided a kind of methane reformer system.Fig. 1 is according to the present invention the The structural representation of one embodiment methane reformer system.As shown in figure 1, a kind of methane reformer system of the present embodiment includes:Hydrogen Separator 1;Heat exchanger 2;Carbon dioxide separation device 3;And solar-energy light collector 4.Wherein, the He of hydrogen separation device 1 Carbon dioxide separation device 3 uses membrane material material separating device.
Fig. 1 is refer to, the medial compartment of hydrogen separation device 1 is divided into two class regions-hydrogen permeation membrane separation side by hydrogen permeation membrane First kind region and hydrogen permeation membrane unstripped gas supply side the second class region.Wherein, the hydrogen dividing potential drop in first kind region is less than first The hydrogen dividing potential drop in the second class region when alkane and steam reforming reaction.
It refer to Fig. 1, the medial compartment of carbon dioxide separation device 3 is divided into two class regions-thoroughly by saturating carbon dioxide membrane 3rd class region of carbon dioxide membrane separation side and the 4th class region of saturating carbon dioxide membrane unstripped gas supply side.Wherein, the 3rd The carbon dioxide partial pressure in saturating 4th class region when the carbon dioxide partial pressure in class region is less than methane and steam reforming.
Fig. 2 is membrane material material separating device schematic diagram in methane reformer system shown in Fig. 1.It refer to Fig. 2, membrane material separation dress Put and middle use barrel forms.More membrane material pipe materials are placed in chamber outer wall 5.The membrane material pipe material is by corresponding membrane material system It is standby, such as:
(1) in hydrogen separation device 1, membrane material pipe material is prepared by hydrogen permeating material, and is internally formed in membrane material pipe material Class two zone domain, first kind region is formed between membrane material pipe material and chamber outer wall.First area can connect vavuum pump or Being passed through inert gas or oxidizing gas reduces hydrogen dividing potential drop;
(2) in carbon dioxide separation device 3, membrane material pipe material is by saturating carbon dioxide film preparation, in membrane material pipe material The 4th class region is internally formed, the 3rd class region is formed between membrane material pipe material and chamber outer wall.3rd class region can connect Connecing vavuum pump or being passed through inert gas or reducibility gas reduces carbon dioxide partial pressure.
In the membrane material material separating device, reacting gas is entered by reaction gas inlet 7, and methane is carried out in membrane material pipe material Reforming reaction, generation gas pass through the product separated region 8 on the outside of membrane material pipe material.
In whole methane reformer system, into the second class region of hydrogen separation device 1 weight occurs for methane and vapor Whole reaction, the hydrogen of generation enter first kind region, and reforming reaction balances to be continued to react to forward direction movement, unreacting gas;And Afterwards, in the second class region reacted gas enter carbon dioxide separation device 3 the 4th class region, separate hydrogen after it is remaining Carbon dioxide enters the 3rd class region;Then, the residual gas in the 4th class region reenters the second of hydrogen separation device 1 Class region.
In the present embodiment, methane and vapor pipeline flow through hydrogen separation device and carbon dioxide separation device and shape successively Into circulation, methane wet reformate hydrogen and carbon dioxide are alternately separated, and promote methane reforming reaction to balance mobile to forward direction, Methane conversion is set significantly to be lifted compared to single reaction conversion ratio.
Wherein, hydrogen separation device 1 and carbon dioxide separation device 3 can be as the reactions of methane and steam reforming Chamber.The operating temperature of hydrogen separation device 1 is greater than the generation temperature of methane and steam reforming reaction, is typically greater than 400 DEG C, but can reduce reaction temperature extremely by way of applying potential difference or ionization reaction thing in methane and steam reforming region More than 100 DEG C.
In the present embodiment, hydrogen separation device and carbon dioxide separation device operation temperature can differ, such as work as hydrogen When air separation is palladium film, saturating hydrogen temperature is typically more than 400 DEG C;Carbon dioxide separation device is organic carbon dioxide separation During film, carbon dioxide separation temperature is generally room temperature, and now can carry out heat by the heat exchanger 2 of connection among pipeline returns Receive.
Fig. 1 is refer to, for heat exchanger 2:Its heater gas inlet port is connected to the gas in the second class region of hydrogen separation device 1 Body exports, and its hot gas outlet is connected to the gas feed in the 4th class region of carbon dioxide separation device 3;Its cold air entrance The gas vent in the 4th class region of carbon dioxide separation device 3 is connected to, the outlet of its cold air is connected to hydrogen separation device 1 The second class region gas feed.
In the present embodiment, by increasing heat exchanger, it can reclaim because hydrogen separation device and carbon dioxide separation device Operation temperature difference caused by thermal losses, the amount of enabling the system to utilization rate lifting.
It is it should be noted that, although wet come methane in piece-rate system using hydrogen permeation membrane and saturating carbon dioxide membrane in the present embodiment Hydrogen caused by reformation and carbon dioxide, but the present invention is not limited thereto.For example:
(1) for hydrogen separation device 1, the mode for separating hydrogen can also be in the inboard cavity of hydrogen separation device 1 Added in room and absorb hydrogen material, such as activated carbon and oxide, now, add the hydrogen dividing potential drop in the region for absorbing hydrogen material just Less than the hydrogen dividing potential drop for not adding the region for absorbing hydrogen material;
(2) for carbon dioxide separation device 3, the mode for reducing carbon dioxide partial pressure is not limited to profit in the present embodiment With the mode of organic carbon dioxide membrane or inorganic carbon dioxide membrane, suction can also be added in carbon dioxide separation device 3 Receive carbon dioxide material, such as alkaline solution, basic anhydride, activated carbon.Now, the region of absorbing carbon dioxide material is added Hydrogen dividing potential drop be less than not adding the carbon dioxide partial pressure in the region of absorbing carbon dioxide material.
Those skilled in the art it should be understood that, in above-mentioned two situations, the change of corresponding partial pressure is consecutive variations, this The division of time domain is also that not real film layer separates two class regions in two chambers in virtual sense.
In the present embodiment, groove type solar concentrator in the second class region of hydrogen separation device 1, incites somebody to action solar light focusing Solar energy is converted to heat energy and supplied needed for reforming reaction therein, but the present invention is not limited thereto.For example:
(1) for solar-energy light collector, Fresnel solar concentrator, disc type solar energy can also be used to gather Light device, or tower type solar concentrator convert solar energy into heat energy;
(2) energy can be provided by solar energy for energy source, the device, can also be by nuclear energy, fossil energy or work Industry used heat provides heat, and energy is provided by solar energy or nuclear energy, it is possible to reduce the use of electric energy and fossil energy, for realizing The sustainable development of the energy is significant.
Low-temperature solar energy is energy source during the present embodiment methane reformer system uses, reaction temperature control 400 DEG C with On.But the present invention is not limited thereto.Also, methane reforming is being reduced using applying electric field to methane weight in wet base whole conversion zone During temperature, operating temperature can just complete the present invention more than 100 DEG C.
The material of hydrogen permeation membrane and saturating carbon dioxide membrane has been well known to those skilled in the art, and is only provided herein several normal Material, by way of example, the one kind of hydrogen permeation membrane material in following material:ZrO2-TiO2-Y2O3;SrCexTm1-xO3-δ (0≤x≤1,0≤δ < 3);SrCexYb1-xO3-α(0≤x≤1,0≤α < 3) and palladium (Pd).Saturating carbon dioxide membrane material is selected from One kind in following material:Adulterate the La of fused carbonate (molten carbonate, similarly hereinafter)1-xSrxCo1-yFeyO3-δ(0 ≤ x≤1,0≤δ < 3);Adulterate Y2O3With the ZrO of fused carbonate2;Adulterate Gd2O3With the CeO of fused carbonate2
It should be noted that, although hydrogen is the main purpose of the present embodiment, but carbon dioxide is also useful.Titanium dioxide Carbon is in great demand medical treatment, chemical industry, oil exploration & development etc..
Further, since inorganic film reactor only allows a kind of gas permeation, therefore the hydrogen and carbon dioxide purity produced It is all very high.Regardless of whether being high-purity hydrogen or high-purity carbon dioxide, value is all very high.Industrial high-volume hydrogen making at present Reacted essentially from gas renormalizing, and the carbon monoxide remained in product is not easy to remove completely;Industrial mass produces dioxy Change carbon and mainly carry out limestone calcination, energy consumption is larger, and energy utilization efficiency is not high.It can be made using the present embodiment methane reformer system Take High Purity Hydrogen, high-purity carbon dioxide seldom to contain other impurity, settle at one go, in energy source and power, medical treatment, chemical industry, oil exploration Etc. it is significant, there is good application value.
In the present embodiment, for whole system using the solar energy focused on as energy source, control device internal temperature is 400 DEG C. When methane and vapor by preheating flow into hydrogen separation device 1, hydrogen can be separated caused by methane and steam reforming Go out system, promote methane weight in wet base is whole to continue that more products are carried out and produced to forward direction.When hydrogen partial pressure decline, carbon dioxide partial pressure After rising, hydrogen partial pressure difference in hydrogen permeation membrane both sides gradually reduces, and the rise of carbon dioxide partial pressure, hinders reaction further to enter to forward direction OK.Mixed gas inflow heat exchanger 2 in hydrogen separation device 1 carries out heat recovery, and continues to flow into carbon dioxide separation dress 3 are put, because now carbon dioxide partial pressure is higher in mixed gas, carbon dioxide separation can be gone out through saturating carbon dioxide membrane and be System, promote methane and vapor further to reform and produce more hydrogen and carbon dioxide.As hydrogen partial pressure raises, carbon dioxide Partial pressure reduces, and methane and steam reforming reaction speed progressively slow down, and are not now separated the admixture of gas of system again Flow into hydrogen separation device 1 and repeat said process until methane and vapor are fully converted to hydrogen and carbon dioxide and is separated Go out system.Hydrogen and carbon dioxide are collected separately.
Fig. 3 is that methane reformer system shown in Fig. 1 circulates methane in hydrogen separation device and titanium dioxide for first 4 at 400 DEG C Remaining proportion in carbon separator.Wherein 1,2,3,4 are illustrated respectively in four circulations methane remaining proportion in hydrogen permeation membrane, 1 ', 2 ', 3 ', 4 ' are illustrated respectively in methane remaining proportion in four circulation carbon dioxide separation devices;
Fig. 4 is that methane reformer system shown in Fig. 1 circulates vapor in hydrogen separation device and dioxy for first 4 at 400 DEG C Change the remaining proportion in carbon separator.Wherein 1,2,3,4 are illustrated respectively in four circulations vapor residue ratio in hydrogen permeation membrane Example, 1 ', 2 ', 3 ', 4 ' are illustrated respectively in vapor remaining proportion in four circulation carbon dioxide separation devices;
By Fig. 3, Fig. 4, it by circulating unreacting gas, can greatly improve methane and steam transforming rate, And conversion ratios are improved to more than 99% after circulation 3 times, and the methane conversion of tradition methane reforming method only has at 400 DEG C 15% or so, by contrast this method have a clear superiority.
Through calculating, methane and vapor after 5 hydrogen separation devices and carbon dioxide separation device, the system Methane and vapor resolution ratio reach more than 99.9%.
2nd, second embodiment
In second exemplary embodiment of the present invention, another low temperature methane reformer system is additionally provided.This is System is with first embodiment difference, by applying potential difference in methane and steam reforming reaction region so that reaction Temperature is drastically reduced near 100 DEG C.Generally, potential difference absolute value delta V meets:0V < Δs V≤1000V.
It should be noted that in addition to using potential difference reduction reaction temperature is applied, ionization reaction thing can also be used Mode reduce reaction temperature, no longer enumerate one by one herein.
So far, two embodiments of the invention are described in detail combined accompanying drawing.According to above description, this area Technical staff should have clear understanding to methane reformer system of the present invention.
It should be noted that in accompanying drawing or specification text, the implementation that does not illustrate or describe is affiliated technology Form known to a person of ordinary skill in the art, is not described in detail in field.In addition, the above-mentioned definition to each element and method is simultaneously Various concrete structures, shape or the mode mentioned in embodiment are not limited only to, those of ordinary skill in the art can carry out letter to it Singly change or replace, such as:
(1) except by setting hydrogen permeation membrane in hydrogen separation device or absorbing hydrogen material, its other party can also be used Formula makes the hydrogen dividing potential drop in first kind region therein less than the hydrogen dividing potential drop in the second class region of another part;
(2) except by centering carbon dioxide membrane or absorbing carbon dioxide material in carbon dioxide separation dress, going back Other modes can be used to make two of carbon dioxide partial pressure less than the 4th class region of another part in the 3rd class region therein Carbonoxide partial pressure;
(3) on absorbing hydrogen material, absorbing carbon dioxide material, hydrogen permeation membrane material, saturating carbon dioxide material, it is not All kinds of specific materials provided in above-described embodiment are provided;
(4) demonstration of the parameter comprising particular value can be provided herein, but these parameters are worth accordingly without being definitely equal to, and It is that can be similar to analog value in acceptable error margin or design constraint;
(5) direction term mentioned in embodiment, such as " on ", " under ", "front", "rear", "left", "right" etc., only it is ginseng The direction of accompanying drawing is examined, is not used for limiting the scope of the invention;
(6) consideration that above-described embodiment can be based on design and reliability, the collocation that is mixed with each other uses or and other embodiment Mix and match uses, i.e., the technical characteristic in different embodiments can freely form more embodiments.
In summary, in methane reformer system of the present invention, pipeline is sequentially connected hydrogen separation device, heat exchanger, titanium dioxide Carbon separator simultaneously reconnects back hydrogen separation device, unstripped gas is flowed through hydrogen separation device, heat exchanger, dioxy successively Change carbon separator, and will not separate gas and flow back to hydrogen separation device again and be circulated.When solution passes through single hydrogen permeation membrane, Suppress the problem of methane reforming reaction is positive mobile because carbon dioxide partial pressure is too high, and methane is improved by circular response Reforming reaction conversion ratio, it is that system capacity utilizes by thermal losses of the heat exchanger recovery because of before and after caused by the device temperature difference Rate is lifted, and has stronger practical value.
Particular embodiments described above, the purpose of the present invention, technical scheme and beneficial effect are carried out further in detail Describe in detail it is bright, should be understood that the foregoing is only the present invention specific embodiment, be not intended to limit the invention, it is all Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc., it should be included in the guarantor of the present invention Within the scope of shield.

Claims (10)

  1. A kind of 1. methane reformer system, it is characterised in that including:
    Hydrogen separation device (1), its medial compartment are divided into first kind region and the second class region, wherein, the hydrogen in first kind region The hydrogen dividing potential drop in the second class region when partial pressure is less than methane and steam reforming reaction;
    Carbon dioxide separation device (3), its medial compartment are divided into the 3rd class region and the 4th class region, wherein, the 3rd class region Carbon dioxide partial pressure the 4th class region when being less than methane and steam reforming reaction carbon dioxide partial pressure, also, the 4th The import in class region is connected to the outlet in the second class region, and the outlet in the 4th class region is connected to the import in the second class region,
    Wherein, methane and vapor enter the second class region of hydrogen separation device (1), and methane reforming reaction occurs, generation Hydrogen enters first kind region, and reforming reaction balances to be continued to react to forward direction movement, unreacting gas;Then, the second class region Interior reacted gas enters the 4th class region of carbon dioxide separation device (3), and remaining carbon dioxide enters after separating hydrogen Enter the 3rd class region;Then, the residual gas in the 4th class region reenters the second class region of hydrogen separation device (1) and entered Row methane reforming reaction.
  2. 2. methane reformer system according to claim 1, it is characterised in that:
    The first kind region, which adds, absorbs hydrogen material, or connection vavuum pump, or is passed through inert gas or oxidizing gas, from And when the hydrogen dividing potential drop in the first kind region is less than methane and steam reforming reaction the second class region hydrogen dividing potential drop;And/or
    The 3rd class region adds absorbing carbon dioxide material, or connection vavuum pump, or is passed through inert gas or reproducibility gas Body so that when the carbon dioxide partial pressure in the 3rd class region is less than methane and steam reforming reaction the 4th class region dioxy Change carbon partial pressure.
  3. 3. methane reformer system according to claim 1, it is characterised in that:
    The medial compartment of the hydrogen separation device (1) is divided into two class regions by hydrogen permeation membrane, wherein, the first kind region is The class region of hydrogen permeation membrane separation side;The second class region is the class region of hydrogen permeation membrane unstripped gas supply side;
    The medial compartment of the carbon dioxide separation device (3) is divided into two class regions by saturating carbon dioxide membrane, wherein, described Three class regions are the class region of saturating carbon dioxide membrane separation side, and the 4th class region is saturating carbon dioxide membrane unstripped gas supply side Class region.
  4. 4. methane reformer system according to claim 1, it is characterised in that also include:Heat exchanger (2), for the heat exchange Device (2):
    Its heater gas inlet port is connected to the gas vent in the second class region, and its hot gas outlet is connected to the gas in the 4th class region Import;
    Its cold air entrance is connected to the gas vent in the 4th class region, and its cold air exports the gas for being connected to the second class region Import.
  5. 5. methane reformer system according to claim 1, it is characterised in that also include:
    Heat provides device, for providing heat for needed for the reforming reaction in the hydrogen separation device (1), its heat is by too Positive energy, nuclear energy, fossil energy or industrial waste heat provide.
  6. 6. methane reformer system according to claim 5, it is characterised in that it is Salar light-gathering that the heat, which provides device, Device (4);
    The solar-energy light collector (4) by solar light focusing in the hydrogen permeation membrane unstripped gas supply side of hydrogen separation device (1), will too Sun can be converted to heat energy for needed for reforming reaction therein.
  7. 7. methane reformer system according to claim 6, it is characterised in that the solar-energy light collector (4) is following One or more combinations:Groove type solar concentrator, tower type solar concentrator, disc type solar energy concentrator and Fresnel Formula solar concentrator.
  8. 8. methane reformer system according to claim 1, it is characterised in that second in the hydrogen separation device (1) The 4th class region in class region and/or the carbon dioxide separation device (3) is as reforming reaction region;
    Wherein, an at least region is included per a kind of region, in reforming reaction region using application potential difference or ionization reaction thing Mode reduce reaction temperature.
  9. 9. according to the methane reformer system any one of claim 3,6,7, it is characterised in that the hydrogen permeation membrane material choosing From one kind in following material:
    ZrO2-TiO2-Y2O3
    SrCexTm1-xO3-δ, wherein 0≤x≤1,0≤δ < 3;
    SrCexYb1-xO3-α, wherein 0≤x≤1,0≤α < 3;With
    Pd。
  10. 10. methane reformer system according to claim 3, it is characterised in that the carbon dioxide membrane material is selected from One kind in following material:
    Adulterate the La of fused carbonate1-xSrxCo1-yFeyO3-δ, wherein 0≤x≤1,0≤δ < 3;
    Adulterate Y2O3With the ZrO of fused carbonate2
    Adulterate Gd2O3With the CeO of doping fused carbonate2
CN201610112216.6A 2016-02-29 2016-02-29 Methane reformer system CN105776133B (en)

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CN107930552A (en) * 2017-11-20 2018-04-20 武汉大学 Solar energy hydrogen permeation membrane reaction unit and application method

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