CN103183317B - Membrane type hydrocarbon recombination hydrogen production device - Google Patents
Membrane type hydrocarbon recombination hydrogen production device Download PDFInfo
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- CN103183317B CN103183317B CN201210085002.6A CN201210085002A CN103183317B CN 103183317 B CN103183317 B CN 103183317B CN 201210085002 A CN201210085002 A CN 201210085002A CN 103183317 B CN103183317 B CN 103183317B
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 347
- 239000001257 hydrogen Substances 0.000 title claims abstract description 347
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 339
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 90
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 90
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 90
- 238000005215 recombination Methods 0.000 title abstract description 100
- 230000006798 recombination Effects 0.000 title abstract description 100
- 239000012528 membrane Substances 0.000 title abstract description 9
- 238000004519 manufacturing process Methods 0.000 title description 69
- 239000012530 fluid Substances 0.000 claims abstract description 82
- 239000007789 gas Substances 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000002407 reforming Methods 0.000 claims abstract 56
- 239000010408 film Substances 0.000 claims description 234
- 238000002485 combustion reaction Methods 0.000 claims description 50
- 229920000642 polymer Polymers 0.000 claims description 21
- 239000000446 fuel Substances 0.000 claims description 19
- 239000010409 thin film Substances 0.000 claims description 18
- 238000001833 catalytic reforming Methods 0.000 claims 2
- 230000002093 peripheral effect Effects 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- 238000000926 separation method Methods 0.000 description 9
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 8
- 102000057593 human F8 Human genes 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 239000003915 liquefied petroleum gas Substances 0.000 description 8
- 229940047431 recombinate Drugs 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 235000009508 confectionery Nutrition 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000002918 waste heat Substances 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 naphtha Substances 0.000 description 2
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- HBVFXTAPOLSOPB-UHFFFAOYSA-N nickel vanadium Chemical compound [V].[Ni] HBVFXTAPOLSOPB-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A membrane hydrocarbon reforming hydrogen producer, comprising: the first reforming section, the first hydrogen filtering membrane section, the second reforming section, the second hydrogen filtering membrane section and the main heat exchanger. The first reforming section is configured to reform the feed to form a first reformed atmosphere. The first hydrogen filtering membrane section is connected with the first recombination section and used for filtering the first recombination atmosphere to form a first product and first residual gas. The second recombination section is connected with the first hydrogen filtering film section and is used for recombining the first residual gas to form a second recombination atmosphere. And the second hydrogen filtering film section is connected with the second recombination section and used for filtering the second recombination atmosphere to form a second product and a second residual gas. The main heat exchanger is connected with the first recombination section and the first hydrogen filtering membrane section, and is connected with the second recombination section and the second hydrogen filtering membrane section. The main heat exchanger can provide hot fluid and cold fluid, wherein the cold fluid is used for cooling the first recombination atmosphere and the second recombination atmosphere before the first recombination atmosphere and the second recombination atmosphere enter the first hydrogen filtering film section and the second hydrogen filtering film section respectively.
Description
Technical field
The invention relates to a kind of hydrogen-producing machine, and relate to a kind of Diaphragm type hydrocarbon recombination hydrogen production device especially.
Background technology
Hydrogen Energy is a kind of energy kenel that the following mankind may use, and its using method is mainly in conjunction with fuel cell power generation or directly burn.Fossil feedstock restructuring is hydrogen production technology main at present, and is difficult in a short time realize owing to reaching extensive ideal of producing hydrogen with the renewable energy resources, and therefore, following 20-30 is still to be reassembled as main product hydrogen technology.
Thin film separation restructuring is one of product hydrogen technology of greatest concern in recent years, it utilizes Hydrogen Separation film to remove in hydrogen autoreaction program, destroy chemical equilibrium and promote the transformation efficiency of reactant, obtaining highly purified hydrogen simultaneously, be beneficial to the performance of fuel battery performance.
But, current modal Hydrogen Separation film-palladium or palladium alloy membrane, can fail gradually in more than 400 degree its strainability changes Celsius, for need to exceed 700 degree Celsius, simultaneously be also main product hydrogen technology Sweet natural gas restructuring for do not mate, therefore, filter hydrogen film to be difficult to and Sweet natural gas recombining reaction connected applications.
Summary of the invention
The invention provides a kind of Diaphragm type hydrocarbon recombination hydrogen production device, it can make recombining reaction and thin film separation mechanism be in optimal service temperature interval separately, with the life-span of the performance and filter hydrogen film that maintain recombining reaction.。
The invention provides a kind of Diaphragm type hydrocarbon recombination hydrogen production device, the fluid of differing temps can be made fully to carry out mutual heat exchange, reach the working temperature that each fluid is suitable.
The invention provides a kind of Diaphragm type hydrocarbon recombination hydrogen production device, effectively can improve transformation efficiency, promote and produce hydrogen rate, and make the purity of the hydrogen of institute's output high.
The present invention proposes a kind of Diaphragm type hydrocarbon recombination hydrogen production device, and its characteristic comprises at what: the first restructuring section, the first filter hydrogen film section, the second restructuring section, the second filter hydrogen film section and main heat exchanger.First recombinates section in order to charging of recombinating, to form the first restructuring atmosphere.First filter hydrogen film section, connects the first restructuring section, in order to filter the first restructuring atmosphere, forms the first product and the first residual air.Second restructuring section, connects the first filter hydrogen film section, in order to the first residual air of recombinating, to form the second restructuring atmosphere.Second filter hydrogen film section, connects the second restructuring section, in order to filter the second restructuring atmosphere, forms the second product and the second residual air.Main heat exchanger, connects the first restructuring section and first and filters hydrogen film section, and connection second restructuring section and second filters hydrogen film section.Main heat exchanger can provide hot-fluid and cold fluid, before wherein cold fluid enters the first filter hydrogen film section and the second filter hydrogen film section respectively in order to atmosphere of recombinating in the first restructuring atmosphere and second, and cooling first restructuring atmosphere and the second restructuring atmosphere.
Above-mentioned according to one embodiment of the invention, being characterised in that of above-mentioned Diaphragm type hydrocarbon recombination hydrogen production device more comprises: the first heat exchanger and the second heat exchanger.First heat exchanger and above-mentioned first section of recombinating is connected, in order to heat above-mentioned charging.Second heat exchanger, filters hydrogen film section and above-mentioned second recombinate that section is above-mentioned to be connected with above-mentioned first, in order to receive above-mentioned first residual air, before above-mentioned first residual air flows into above-mentioned second restructuring section, heat it.
Above-mentioned according to one embodiment of the invention, above-mentioned Diaphragm type hydrocarbon recombination hydrogen production device be characterised in that above-mentioned charging enters above-mentioned first heat exchanger before, first by above-mentioned main heat exchanger, with the above-mentioned hot fluid heats through above-mentioned main heat exchanger.
Above-mentioned according to one embodiment of the invention, being characterised in that of above-mentioned Diaphragm type hydrocarbon recombination hydrogen production device more comprises: the 3rd restructuring section, in order to above-mentioned second residual air of recombinating, to form the 3rd restructuring atmosphere; 3rd filter hydrogen film section, in order to filter above-mentioned 3rd restructuring atmosphere, forms third product and the 3rd residual air; 3rd heat exchanger, filter hydrogen film section and the above-mentioned 3rd recombinate that section is above-mentioned to be connected with above-mentioned second, in order to receive above-mentioned second residual air, it was heated before above-mentioned second residual air flows into above-mentioned 3rd restructuring section, and above-mentioned 3rd restructuring atmosphere is before entering above-mentioned 3rd filter hydrogen film section, be introduced into above-mentioned main heat exchanger, with the above-mentioned 3rd restructuring atmosphere of above-mentioned cold fluid cooling.
Above-mentioned according to one embodiment of the invention, above-mentioned Diaphragm type hydrocarbon recombination hydrogen production device be characterised in that above-mentioned first restructuring section and above-mentioned first filter between hydrogen film section separate, above-mentioned first filter hydrogen film and above-mentioned second is recombinated separate between section, above-mentioned second restructuring section and above-mentioned second is filtered between hydrogen film separate, above-mentioned second filter hydrogen film and the above-mentioned 3rd is recombinated separate between section, above-mentioned 3rd restructuring section and the above-mentioned 3rd is filtered between hydrogen film separate, and respectively with flow passage.
Above-mentioned according to one embodiment of the invention, above-mentioned Diaphragm type hydrocarbon recombination hydrogen production device be characterised in that above-mentioned charging enters above-mentioned first heat exchanger before, first by above-mentioned main heat exchanger, with the above-mentioned hot fluid heats through above-mentioned main heat exchanger.
Above-mentioned according to one embodiment of the invention, being characterised in that of above-mentioned Diaphragm type hydrocarbon recombination hydrogen production device comprises above-mentioned charging by the above-mentioned cold fluid of above-mentioned main heat exchanger.
Above-mentioned according to one embodiment of the invention, being characterised in that of above-mentioned Diaphragm type hydrocarbon recombination hydrogen production device comprises the above-mentioned first restructuring atmosphere flowed out from above-mentioned first restructuring section, the above-mentioned second restructuring atmosphere flowed out from above-mentioned second restructuring section, the above-mentioned 3rd restructuring atmosphere that flows out from above-mentioned 3rd restructuring section by the above-mentioned hot-fluid of above-mentioned main heat exchanger, and carries out heat exchange by the above-mentioned hot-fluid of above-mentioned main heat exchanger and above-mentioned charging.
Above-mentioned according to one embodiment of the invention, being characterised in that of above-mentioned Diaphragm type hydrocarbon recombination hydrogen production device more comprises: main heat exchange zone, methanation region, thin film region, combustion zone and preheating zone.Above-mentioned main heat exchanger is arranged in above-mentioned heat exchange zone.Methanation region, is positioned at above above-mentioned main heat exchange zone, or filters hydrogen film section, above-mentioned second and filter the outlet that hydrogen film section and the above-mentioned 3rd filters hydrogen film section product with above-mentioned first and be connected.Thin film region, above-mentioned first filter hydrogen film section, above-mentioned second filter hydrogen film section and the above-mentioned 3rd are filtered hydrogen film section and are arranged in above-mentioned thin film region.Combustion zone, is provided with a burner; One recombination zone, is surrounded on the top or around of above-mentioned combustion zone, above-mentioned first restructuring section, above-mentioned second restructuring section and above-mentioned 3rd restructuring section, is separately arranged in above-mentioned recombination zone.Preheating zone, be positioned at outside the fluid outlet of periphery, above-mentioned recombination zone and above-mentioned methanation region, above-mentioned first heat exchanger, the second heat exchanger and above-mentioned 3rd heat exchanger are arranged in the above-mentioned preheating zone of periphery, above-mentioned recombination zone.
Above-mentioned according to one embodiment of the invention, above-mentioned Diaphragm type hydrocarbon recombination hydrogen production device be characterised in that above-mentioned 3rd residual air produced by above-mentioned 3rd filter hydrogen film section is back to above-mentioned combustion chamber.
Above-mentioned according to one embodiment of the invention, being characterised in that of above-mentioned Diaphragm type hydrocarbon recombination hydrogen production device more comprises the 4th heat exchanger, is arranged in the above-mentioned preheating zone of above-mentioned methanation region fluid outlet.
Above-mentioned according to one embodiment of the invention, above-mentioned Diaphragm type hydrocarbon recombination hydrogen production device be characterised in that the hot-fluid of above-mentioned 4th heat exchanger above-mentioned first product formed that comprises above-mentioned first filter hydrogen film section, burning gas that above-mentioned second product that above-mentioned second filter hydrogen film section is formed or the above-mentioned third product that above-mentioned 3rd filter hydrogen film section is formed, combustion chamber produce, the cold fluid of above-mentioned 4th heat exchanger comprises above-mentioned charging, the air of burning and fuel.
Above-mentioned according to one embodiment of the invention, being characterised in that of above-mentioned Diaphragm type hydrocarbon recombination hydrogen production device more comprises the 4th heat exchanger, the burning gas that above-mentioned second product that the hot-fluid of above-mentioned 4th heat exchanger comprises above-mentioned first product that above-mentioned first filter hydrogen film section formed, above-mentioned second filter hydrogen film section is formed, combustion chamber produce, the cold fluid of above-mentioned 4th heat exchanger comprises above-mentioned charging, the air of burning and fuel.
The present invention proposes again a kind of Diaphragm type hydrocarbon recombination hydrogen production device, comprises the first restructuring section, the first filter hydrogen film section, the second restructuring section, the second filter hydrogen film section, the first heat exchanger and the second heat exchanger.First restructuring section, in order to charging of recombinating, to form the first restructuring atmosphere.First filter hydrogen film section, in order to filter the first restructuring atmosphere, forms the first product and the first residual air.Second restructuring section, in order to the first residual air of recombinating, to form the second restructuring atmosphere.Second filter hydrogen film section, in order to filter the second restructuring atmosphere, forms the second product and the second residual air.First heat exchanger, is connected, in order to add hot feed with the first section of recombinating.Second heat exchanger, filters hydrogen film section and second section of recombinating be connected with first, in order to receive the first residual air, before the first residual air flows into the second restructuring section, heat it.
Above-mentioned according to one embodiment of the invention, being characterised in that of above-mentioned Diaphragm type hydrocarbon recombination hydrogen production device more comprises: the 3rd restructuring section, the 3rd filter hydrogen film section and the 3rd heat exchanger.3rd restructuring section, in order to above-mentioned second residual air of recombinating, to form the 3rd restructuring atmosphere.3rd filter hydrogen film section, in order to filter above-mentioned 3rd restructuring atmosphere, forms third product and the 3rd residual air.3rd heat exchanger, filters hydrogen film section and the above-mentioned 3rd recombinate that section is above-mentioned to be connected with above-mentioned second, in order to receive above-mentioned second residual air, before above-mentioned second residual air flows into above-mentioned 3rd restructuring section, heat it.
Above-mentioned according to one embodiment of the invention, above-mentioned Diaphragm type hydrocarbon recombination hydrogen production device be characterised in that above-mentioned first restructuring section and above-mentioned first filter between hydrogen film section separate, above-mentioned first filter hydrogen film and above-mentioned second is recombinated separate between section, above-mentioned second restructuring section and above-mentioned second is filtered between hydrogen film separate, above-mentioned second filter hydrogen film and the above-mentioned 3rd is recombinated separate between section, above-mentioned 3rd restructuring section and the above-mentioned 3rd is filtered between hydrogen film separate, and respectively with flow passage.
Above-mentioned according to one embodiment of the invention, being characterised in that of above-mentioned Diaphragm type hydrocarbon recombination hydrogen production device more comprises combustion chamber, wherein above-mentioned first restructuring section is positioned at above above-mentioned combustion chamber, above-mentioned second restructuring section and the above-mentioned 3rd section of recombinating is surrounded on around above-mentioned combustion chamber, and above-mentioned second heat exchanger and above-mentioned second heat exchanger are surrounded on the above-mentioned second section and the above-mentioned 3rd of recombinating and recombinate section periphery.
Above-mentioned according to one embodiment of the invention, above-mentioned Diaphragm type hydrocarbon recombination hydrogen production device be characterised in that above-mentioned 3rd residual air produced by above-mentioned 3rd filter hydrogen film section is back to above-mentioned combustion chamber.
Above-mentioned according to one embodiment of the invention, being characterised in that of above-mentioned Diaphragm type hydrocarbon recombination hydrogen production device more comprises the 4th heat exchanger, the burning gas that above-mentioned second product that the hot-fluid of above-mentioned 4th heat exchanger comprises above-mentioned first product that above-mentioned first filter hydrogen film section produces, above-mentioned second filter hydrogen film section produces or the above-mentioned third product that above-mentioned 3rd filter hydrogen film section produces, combustion chamber produce, the cold fluid of above-mentioned 4th heat exchanger comprises above-mentioned charging, the air of burning and fuel.
Based on above-mentioned, the Diaphragm type hydrocarbon recombination hydrogen production device of the embodiment of the present invention, can make recombining reaction and thin film separation mechanism be in optimal service temperature interval separately, with the life-span of the performance with filter hydrogen film that maintain recombining reaction.
The Diaphragm type hydrocarbon recombination hydrogen production device of the embodiment of the present invention, can make the temperature increase of charging and the residual air after filter hydrogen film section, reach the service temperature of the recombining reaction being suitable for restructuring section.
The Diaphragm type hydrocarbon recombination hydrogen production device of the embodiment of the present invention, can make the temperature through the reacted restructuring atmosphere of restructuring section reduce, reach the service temperature being suitable for filtering hydrogen film section.
The Diaphragm type hydrocarbon recombination hydrogen production device of the embodiment of the present invention has at least two group restructuring sections and effectively can promote transformation efficiency with filter hydrogen film section, promotes and produces hydrogen rate, and make the purity of the hydrogen of institute's output high.
For above-mentioned feature and advantage of the present invention can be become apparent, special embodiment below, and coordinate institute's accompanying drawings to be described in detail below.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of a kind of Diaphragm type hydrocarbon recombination hydrogen production device that the foundation embodiment of the present invention illustrates.
Fig. 2 is the partial perspective view of the main heat exchanger of a kind of Diaphragm type hydrocarbon recombination hydrogen production device that the foundation embodiment of the present invention illustrates.
Fig. 3 is the diagrammatic cross-section of the main heat exchanger of Fig. 2.
Fig. 4 is the rough schematic in a kind of Diaphragm type hydrocarbon recombination hydrogen production device Zhong Ge district that foundation one embodiment of the invention illustrates.
Fig. 5 is the detailed maps of a kind of Diaphragm type hydrocarbon recombination hydrogen production device that foundation one embodiment of the invention illustrates.
Fig. 6 is the sectional view of the recombination zone of the Diaphragm type hydrocarbon recombination hydrogen production device that foundation one embodiment of the invention illustrates.
Fig. 7 is the top view of the first restructuring section of the Diaphragm type hydrocarbon recombination hydrogen production device that foundation one embodiment of the invention illustrates.
Fig. 8 is the second restructuring section of the Diaphragm type hydrocarbon recombination hydrogen production device that foundation one embodiment of the invention illustrates and the top view of the 3rd restructuring section.
Fig. 9 is the diagrammatic cross-section of the second restructuring Duan Yu tri-section of restructuring of the Diaphragm type hydrocarbon recombination hydrogen production device that foundation one embodiment of the invention illustrates.
Figure 10 is the top view of the thin film region of the Diaphragm type hydrocarbon recombination hydrogen production device that foundation one embodiment of the invention illustrates.
Description of reference numerals
10,50: Diaphragm type hydrocarbon recombination hydrogen production device
12: combustion chamber
14: main heat exchanger
16: heat exchanger set
16a: the first heat exchanger
16b: the second heat exchanger
16c: the three heat exchanger
16d: the four heat exchanger
18: restructuring section group
18a: the first restructuring section
18b: the second restructuring section
18c: the three restructuring section
19: opening for feed
20: filter hydrogen film section group
20a: the first filter hydrogen film section
20b: the second filter hydrogen film section
20c: the three filter hydrogen film section
21: feed-pipe
22,24,30,34,38,39,40,41: outlet
23,28,32,35,36,37: entrance
26: passage
100: main heat exchange zone
200: methanation region
300: thin film region
500: combustion zone
400: recombination zone
600,600a, 600b, 600c: preheating zone
Embodiment
Fig. 1 is the schematic diagram of a kind of Diaphragm type hydrocarbon recombination hydrogen production device of the embodiment of the present invention.
Please refer to Fig. 1, Diaphragm type hydrocarbon recombination hydrogen production device 10 comprises combustion chamber 12, main heat exchanger 14, heat exchanger set 16, restructuring section group 18 and filter hydrogen film section group 20.Heat exchanger set 16 of the present invention, restructuring section group 18, filter hydrogen film section group 20, comprise at least two heat exchangers, at least two restructuring sections, at least two filter hydrogen film sections respectively.For convenience of description, the present embodiment comprises the first heat exchanger 16a, the second heat exchanger 16b and the 3rd heat exchanger 16c with heat exchanger set 16; Restructuring section group 18 comprises the first restructuring section 18a, the second restructuring section 18b and the 3rd recombinates section 18c; Filter hydrogen film section group 20 comprises the first filter hydrogen film section 20a, the second filter hydrogen film section 20b and the 3rd filters hydrogen film section 20c and illustrates.But the present invention is not limited to this.
In the embodiment of the present invention, the first restructuring section 18a and first filters between hydrogen film section 20a separate, is communicated with 54 with runner 52.First filter hydrogen film 20a and second recombinates separate between section 18b, is communicated with runner 56.Second restructuring section 18b and second filters between hydrogen film 20b separate, is communicated with 60 with runner 58.Second filter hydrogen film 20b and the 3rd recombinates separate between section 18c, is communicated with runner 62.3rd restructuring section 18c and the 3rd filters between hydrogen film 20c separate, and is communicated with 66 with runner 64.
The recombinant gas that the operable charging of Diaphragm type hydrocarbon recombination hydrogen production device 10 of the present invention is formed after can being included in and carrying out recombining reaction has higher temperature person, such as, be film (being such as palladium or palldium alloy) the tolerant temperature limitation person higher than filter hydrogen film section.Charging is such as the mixture comprising hydrocarbon polymer and water.Hydrocarbon polymer comprises fossil feedstock or the renewable energy resources.Fossil feedstock be such as Sweet natural gas, liquefied petroleum gas (LPG) (liquefied petroleum gas, LPG), naphtha, kerosene or diesel oil etc. containing the material such as alkanes or alkene class, also can be higher alcohols class or the ethers such as ethanol, propyl alcohol, dme; The renewable energy resources are such as the methane that anaerobic reaction produces or the hydrocarbon polymer of giving birth to many carbon such as matter ethanol, butanols.In one embodiment, the fuel producing heat in order to burning is such as that Sweet natural gas, liquefied petroleum gas (LPG), naphtha, kerosene or diesel oil etc. contain the material such as alkanes or alkene class, also can be alcohols or the ethers such as methyl alcohol, ethanol, propyl alcohol, dme.
Above-mentioned combustion chamber 12 in order to combustion fuel and air, to form burning gas (Flue gas), to be supplied to the first heat exchanger 16a, the second heat exchanger 16b and the 3rd heat exchanger 16c as hot-fluid.Fuel is such as Sweet natural gas or liquefied petroleum gas (LPG).In one embodiment, combustion air, fuel and recombining reaction charging can utilize after the 4th heat exchanger 16d does heat exchange with the hydrogen of output and burning gas, then enter main heat exchanger 14.In one embodiment, from the residual air that final stage filter hydrogen section (the present embodiment is the 3rd filter hydrogen section 20c) flows out, its temperature is about between 300 degree to 500 degree Celsius, can be back to combustion chamber 12, or passes in the 4th heat exchanger as hot-fluid.
Main heat exchanger 14 can provide hot-fluid and cold fluid, to heat or the use of cooling.Hot-fluid in main heat exchanger 14 comprises the first restructuring atmosphere flowed out from the first restructuring section 18a, the second restructuring atmosphere flowed out from the second restructuring section 18b, or the 3rd restructuring atmosphere that the 3rd restructuring section 18c flows out.Cold fluid in main heat exchanger 14 comprises charging.
Fig. 2 is the partial perspective view of the main heat exchanger of a kind of Diaphragm type hydrocarbon recombination hydrogen production device of the embodiment of the present invention.Fig. 3 is the diagrammatic cross-section of the main heat exchanger of Fig. 2.
Please refer to Fig. 2 and Fig. 3, in one embodiment, the charging of room temperature its can as the cold fluid of main heat exchanger 14; And in main heat exchanger 14 from first restructuring section 18a flow out first restructuring atmosphere, from second restructuring section 18b flow out second restructuring atmosphere, or can as hot-fluid from the 3rd restructuring atmosphere of restructuring section the 3rd restructuring section 18c outflow, cold fluid and hot-fluid can carry out heat exchange.In other words, by the charging of main heat exchanger 14, its can cool in main heat exchanger 14 from first restructuring section 18a flow out first restructuring atmosphere, from second restructuring section 18b flow out second restructuring atmosphere, or the temperature of the 3rd restructuring atmosphere that section 18c flows out of recombinating from restructuring section the 3rd, with reduce the first restructuring atmosphere entering the first filter hydrogen film section 20a temperature, enter the second filter hydrogen film section 20b the second restructuring atmosphere temperature with enter the 3rd and filter the 3rd of hydrogen film section 20c and to recombinate the temperature of atmosphere.Charging then can the preheating because of the first restructuring atmosphere, the second restructuring atmosphere and the 3rd restructuring atmosphere.
First heat exchanger 16a is directly connected with combustion chamber 12, and also directly can be connected with main heat exchanger 14, it is add hot feed.The hot-fluid of the first heat exchanger 16a is such as the hot burning gas from combustion chamber 12.By the burning gas after the first heat exchanger 16a, then flow into the 4th heat exchanger 16d, to reclaim its waste heat.The temperature of the hot-fluid that the first heat exchanger 16a provides is such as 500 degree to 900 degree Celsius Celsius.
First restructuring section 18a, can carry out the recombining reaction producing hydrogen.More particularly, the first restructuring section 18a is connected with the first heat exchanger 16a, and the charging restructuring that can will be heated by the first heat exchanger 16a, to form the first restructuring atmosphere.In an exemplary embodiment, charging is methane and water, after the first restructuring section 18a restructuring, methane can be reassembled as and comprise hydrogen, carbon monoxide, carbonic acid gas, atmosphere of recombinating with first of unreacted methane and water.
The temperature of the first restructuring atmosphere that the first restructuring section 18a flows out is such as 450 degree to 700 degree Celsius, and after the cooling of its cold fluid via main heat exchanger 14, it is such as 300 degree to 500 degree Celsius that its temperature can be reduced to.
First filter hydrogen film section 20a system is in order to hydrogen in atmosphere and other product separations of recombinating first.The first product after the first filter hydrogen film section 20a separation and purification is sent via different discharge ports respectively from the first residual air.The first product that first filter hydrogen film section 20a sends first by methanation section 15, by the methanation of carbon monoxide in the hydrogen of the first product, afterwards, then can do various application according to demand.The fluid (the first residual air) that first filter hydrogen film section 20a flows out then can as the reactant of the second restructuring section 18b.
Second heat exchanger 16b can heat the fluid (the first residual air) flowed out from the first filter hydrogen film section 20a, enters the second restructuring section 18b after making its temperature increase again.In one embodiment, be such as 300 degree to 500 degree Celsius from the first temperature of filtering the fluid (the first residual air) that hydrogen film section 20a flows out, after the second heat exchanger 16b heats, its temperature can be promoted to 450 degree to 700 degree Celsius Celsius.The hot-fluid of the second heat exchanger 16b is such as the hot burning gas from combustion chamber 12.By the burning gas after the second heat exchanger 16b, then flow into the 4th heat exchanger 16d, to reclaim its waste heat.The temperature of hot-fluid is such as 500 degree to 900 degree Celsius Celsius.
Second restructuring section 18b, is connected with the second heat exchanger 16b, in order to restructuring from above-mentioned first filter hydrogen film section 20a to flow out and by the fluid of the second heat exchanger 16b, to form the second restructuring atmosphere.In an exemplary embodiment, charging is methane and water, and methane can be reassembled as and comprise hydrogen, carbon monoxide, carbonic acid gas, atmosphere of recombinating with first of unreacted methane and water by the first restructuring section 18a; Unreacted methane and water in the middle of the first residual air that first restructuring section 18a can flow out by the second restructuring section 18b, be reassembled as and comprise hydrogen, carbon monoxide, carbonic acid gas, atmosphere of recombinating with second of unreacted methane and water.
The temperature of the second restructuring atmosphere that the second restructuring section 18b flows out is such as 450 degree to 700 degree Celsius, and after the cold fluid cooling via main heat exchanger 14, its temperature can be down to 300 degree to 500 degree Celsius, and it can flow into the second filter hydrogen film section 20b again.
Second filters hydrogen film section 20b system in order to filter the second restructuring atmosphere, by hydrogen wherein and other product separations.The second product obtained after separation and purification is sent via different discharge ports from the second residual air.Second product first can pass through methanation section 15, by the methanation of carbon monoxide in the hydrogen of the second product, afterwards, does various application according to demand.The temperature of the fluid (the second residual air) that the second filter hydrogen film section 20b flows out is such as 300 degree to 500 degree Celsius, and it is via after the 3rd heat exchanger 16c heat temperature raising, can again as the reactant passing into the 3rd restructuring section 18c.The hot-fluid of the 3rd heat exchanger 16c is such as the hot burning gas from combustion chamber 12.By the burning gas after the 3rd heat exchanger 16c, then flow into the 4th heat exchanger 16d, to reclaim its waste heat.The temperature of hot-fluid is such as 500 degree to 900 degree Celsius Celsius.
From the fluid that the second filter hydrogen film section 20b flows out, after the 3rd heat exchanger 16c heat temperature raising, enter after the 3rd restructuring section 18c recombinates, form the 3rd restructuring atmosphere.The 3rd temperature of recombinating atmosphere flowed out from the 3rd restructuring section 18c is such as 450 degree to 700 degree Celsius, and after the cooling of its cold fluid via main heat exchanger 14, temperature can be down to 300 degree to 500 degree Celsius, then, can flow into the 3rd filter hydrogen film section 20c again.
3rd filter hydrogen film section 20c can filter the 3rd restructuring atmosphere, and form third product and the 3rd residual air to filter, third product is sent via different discharge ports from the 3rd residual air.Third product first can pass through methanation section 15, by the methanation of carbon monoxide in the hydrogen of third product, afterwards, does various application according to demand.The temperature of the 3rd residual air that 3rd filter hydrogen film section 20c (the filter hydrogen film section of least significant end) leaches is such as 300 degree to 500 degree Celsius, and it can reverse flow type combustor 12, as the fuel of combustion chamber 12.
Above-mentioned first filter hydrogen film section 20a, the second filter hydrogen film section 20b and the 3rd filter hydrogen film section 20c and the cavity filtering hydrogen film are housed.The material of filter hydrogen film can be identical or different, and its material can be metal or metal alloy, such as, be pure palladium, palladium-silver alloy, palladium-copper alloy, vananum, vanadium nickel alloy or vanadium palldium alloy.First filter hydrogen film section 20a, second filters hydrogen film section 20b can be identical or different with the 3rd cavity volume filtering hydrogen film section 20c, and wherein contained filter hydrogen film size also can be identical or different.First restructuring atmosphere, the second restructuring atmosphere and the 3rd recombinate atmosphere be all lower the temperature via the cold fluid of main heat exchanger 14 after just enter the first filter hydrogen film section 20a, second and filter hydrogen film section 20b and the 3rd and filter hydrogen film section 20c.Owing to entering the first filter hydrogen film section 20a, the second filter hydrogen film section 20b and the 3rd filters first of hydrogen film section 20c atmosphere, second of recombinating and recombinates that to recombinate that the temperature of atmosphere can be reduced to be such as 300 degree to 500 degree Celsius to atmosphere and the 3rd, therefore, when the material that the first filter hydrogen film section 20a, the second filter hydrogen film section 20b and the 3rd filter hydrogen film section 20c is the materials such as pure palladium, palladium-silver alloy, palladium-copper alloy, the problem not having hydrogen embrittlement produces.
In addition, the gas (product) filtered out from the first filter hydrogen film section 20a, the gas (product) filtered out from the second filter hydrogen film section 20b or the gas (product) filtered out from the 3rd filter hydrogen film section 20c, after methanation, above-mentioned product component is such as hydrogen, methane, water vapour, carbonic acid gas or carbon monoxide, wherein the concentration of hydrogen is less than 20ppm between 90 ~ 99.9vol%, CO concentration.Above-mentioned all product temperatur are such as 300 degree to 500 degree Celsius, first can utilize the hot-fluid as adding hot feed, or as the air of preheated burning or the hot-fluid of fuel or both mixtures, afterwards, doing various application according to demand again, such as, is the use etc. as the hydrogenation reaction in the fuel of fuel cell or chemical reaction.
First restructuring section 18a, the second restructuring section 18b and the 3rd section 18c that recombinates can be the cavity of filler metal catalyst or nonmetal catalyst.The recombinate cavity of section 18c of first restructuring section 18a, the second restructuring section 18b and the 3rd can be separate, only transmits runner and communicates with each other.In addition, the first restructuring section 18a, the second restructuring section 18b and the 3rd recombinates the cavity volume of section 18c can be identical or different, and the catalyst amount of filling also can be identical or different.
In embodiments of the present invention, first restructuring section 18a, second restructuring section 18b, 3rd restructuring section 18c and first filters hydrogen film section 20a, second filter hydrogen film section 20b, the gap of the 3rd filter hydrogen film section 20c is through flow passage, instead of contact of fitting each other, therefore, even if from the first restructuring atmosphere that the first restructuring section 18a flows out, from second restructuring section 18b flow out second restructuring atmosphere and from the 3rd restructuring section 18c flow out the 3rd restructuring atmosphere temperature very high, also can not to the first filter hydrogen film section 20a, second filter hydrogen film section 20b, 3rd filter hydrogen film section 20c directly heats.Moreover, all can lower the temperature through the cold fluid of main heat exchanger 14 before the first restructuring atmosphere, the second restructuring atmosphere and the 3rd restructuring atmosphere enter the first filter hydrogen film section 20a, the second filter hydrogen film section 20b, the 3rd filter hydrogen film section 20c, therefore, can guarantee that the first filter hydrogen film section 20a, the second filter hydrogen film section 20b, the 3rd filter hydrogen film section 20c maintain good strainability.
Moreover, charging, the fluid flowed out from the first filter hydrogen film section 20a, the fluid that flows out from the second filter hydrogen film section 20b enter that the first restructuring section 18a, second recombinates with the section 18b, the 3rd that recombinates also can via the hot fluid heats of the first heat exchanger 16a, the second heat exchanger 16b, the 3rd heat exchanger 16c before section 18c, therefore, it can be made to reach service temperature needed for recombining reaction.
In embodiments of the present invention, by the burning gas after the first heat exchanger 16a, the second heat exchanger 16b and the 3rd heat exchanger 16c, before inflow the 4th heat exchanger 16d, capital first contacts with the housing surface of filter hydrogen film section, to heat the first filter hydrogen film section 20a, the second filter hydrogen film section 20b or the 3rd filter hydrogen film section 20c.
Diaphragm type hydrocarbon recombination hydrogen production device due to this case comprises the restructuring section of at least two groups and filter hydrogen film section, therefore, by program repeatedly, effectively can promote transformation efficiency, and obtain the hydrogen of purity between 90 ~ 99.9vol%.
Fig. 4 is the rough schematic in a kind of Diaphragm type hydrocarbon recombination hydrogen production device Zhong Ge district that foundation one embodiment of the invention illustrates.Fig. 5 is the detailed maps of a kind of Diaphragm type hydrocarbon recombination hydrogen production device that foundation one embodiment of the invention illustrates.
Please refer to Fig. 4, Diaphragm type hydrocarbon recombination hydrogen production device 50 comprises main heat exchange zone 100, methanation region 200, thin film region 300, combustion zone 500, recombination zone 400 and preheating zone 600.
Please refer to Fig. 4 and 5, combustion zone 500 is positioned at the lower central part of Diaphragm type hydrocarbon recombination hydrogen production device 50, in order to arrange above-mentioned combustion chamber 12.
Preheating zone 600 comprises preheating zone 600a, 600b and 600c, and wherein preheating zone 600a is positioned at above the methanation region 200 on the top of Diaphragm type hydrocarbon recombination hydrogen production device 50, and the 4th above-mentioned heat exchanger 16d is arranged among the 600a of this preheating zone; Preheating zone 600b is positioned at the bottom of Diaphragm type hydrocarbon recombination hydrogen production device 50, and is positioned at above combustion zone 500, and the first above-mentioned heat exchanger 16a is arranged among the 600b of this preheating zone and (does not show the first heat exchanger 16a in Fig. 5); The bottom that preheating zone 600c is positioned at Diaphragm type hydrocarbon recombination hydrogen production device 50 is surrounded on around recombination zone 400, and the second above-mentioned heat exchanger 16b, the 3rd heat exchanger 16c, be arranged among the 600c of this preheating zone.
Main heat exchange zone 100 is positioned at the central upper portion part of Diaphragm type hydrocarbon recombination hydrogen production device 50, under preheating zone 600a and methanation region 200.Above-mentioned main heat exchanger 14 is arranged in this main heat exchange zone 100, does heat exchange in order to provide hot-fluid and cold fluid.
Recombination zone 400 is positioned at the bottom of Diaphragm type hydrocarbon recombination hydrogen production device 50, that is the below of main heat exchange zone 100, and it is positioned at the top of combustion zone 500 and combustion zone 500 around.In one embodiment, above-mentioned restructuring section group 18 comprises the first restructuring section 18a, the second restructuring section 18b and the 3rd recombinates section 18c, and it is arranged among this recombination zone 400.
Fig. 6 is the sectional view of the recombination zone of the Diaphragm type hydrocarbon recombination hydrogen production device of one embodiment of the invention.Fig. 7 is the top view of the first restructuring section of the Diaphragm type hydrocarbon recombination hydrogen production device of one embodiment of the invention.Fig. 8 is the second restructuring section of the Diaphragm type hydrocarbon recombination hydrogen production device of one embodiment of the invention and the top view of the 3rd restructuring section.
Please refer to Fig. 5,6, the first restructuring section 18a is arranged in the recombination zone 400 above combustion zone 500; Second restructuring section 18b and the 3rd restructuring section 18c is surrounded in the recombination zone 400 around combustion zone 500, and wherein the second restructuring section 18b is arranged in the recombination zone 400 of side, combustion zone 500; 3rd restructuring section 18c is arranged in the recombination zone 400 of the opposite side of combustion zone 500.
Please refer to Fig. 6,7, the first restructuring section 18a has the entrance 23 of charging and the outlet 24 of the first restructuring atmosphere.First restructuring section 18a also has multiple passage 26, hot gas flow up can be flowed by bottom, as shown in Figure 7.The number of passage 26 and shape, there is no particular restriction, is not limited with graphic.
Please refer to Fig. 5,6-8, the second restructuring section 18b has the entrance 28 that charging enters the second restructuring section 18b, and the outlet 30 of the second restructuring atmosphere.The outlet 30 of the second restructuring section 18b through one of them passage 26 of the first restructuring section 18a laggard enter main heat exchanger 14.3rd restructuring section 18c have charging enter the 3rd restructuring section 18b entrance 32, and via the 3rd restructuring section 18c produce the 3rd restructuring atmosphere outlet 34.The outlet 34 of the 3rd restructuring section 18c through another passage 26 of the first restructuring section 18a laggard enter main heat exchanger 14.
Fig. 9 is that the second restructuring section 18b and the 3rd of the Diaphragm type hydrocarbon recombination hydrogen production device of the embodiment of the present invention recombinates the diagrammatic cross-section of the runner in section 18c.Please refer to Fig. 8,9, the second restructuring section 18b and the 3rd runner of recombinating in section 18c can be cut into multistage, can go up current downflow to make fluid.In one embodiment, the second restructuring section 18b and the 3rd section 18c that recombinates in recombination zone 400 can be cut into three sections, the entrance 28 or 32 of fluid bottom the first lattice enters, from bottom to top follow compartment and enter the second lattice, from top to bottom flow at the second lattice, from bottom to top flow to the 3rd lattice, then left by the outlet 30 or 34 above the 3rd lattice.But in recombination zone, the second restructuring section 18b and the 3rd section 18c that recombinates also can be cut into more than three sections to go up current downflow, also can not make compartment, directly flow from lower to upper.
Please refer to Fig. 4,5, thin film region 300 is positioned at the top of Diaphragm type hydrocarbon recombination hydrogen production device 50, and is surrounded on around heat exchange zone 100, and above-mentioned filter hydrogen film section group 20 is arranged in this thin film region 300.
Figure 10 is the top view of the thin film region of the Diaphragm type hydrocarbon recombination hydrogen production device of one embodiment of the invention.
Please refer to Figure 10, in one embodiment, the filter hydrogen film section group 20 arranged in thin film region 300 comprises the first filter hydrogen film section 20a, the second filter hydrogen film section 20b and the above-mentioned 3rd filters hydrogen film section 20c.First filter hydrogen film section 20a, the second filter hydrogen film section 20b and the above-mentioned 3rd filter hydrogen film section 20c and can adjust its area according to actual demand, and the filter hydrogen film size of three can be identical or different.First filters hydrogen film section 20a, the second filter hydrogen film section 20b and the above-mentioned 3rd filters hydrogen film section 20c its entrance and outlet separately.Please refer to figure Fig. 5, the first filter hydrogen film section 20a comprises entrance 36 and outlet 38, second and filter hydrogen film section 20b and comprise entrance 37 and filter hydrogen film section 20c with outlet the 40, three and comprise entrance 35 and export 41.
First restructuring section 18a and first filters between hydrogen film section 20a separate, to export the flow passage between 24 to entrance 36.First filter hydrogen film 20a and second recombinates separate between section 18b, to export the flow passage between 38 and entrance 28.Second restructuring section 18b and second filters between hydrogen film 20b separate, to export the flow passage between 30 to the entrance 37 entering the second filter hydrogen film 20b.Second filter hydrogen film 20b and the 3rd recombinates separate between section 18c, to export the flow passage between 40 and entrance 32.3rd restructuring section 18c and the 3rd filter between hydrogen film 20c separate, and to export 34 to the flow passage entered between the 3rd entrance 35 filtering hydrogen film 20c.
Methanation region 200 is positioned at the top of Diaphragm type hydrocarbon recombination hydrogen production device 50, i.e. the top of main heat exchange zone 100.Methanation region 200 arranges above-mentioned methanation section 15, wherein has catalyst, in order to the first filter hydrogen film section 20a, the second filter hydrogen film section 20b and the above-mentioned 3rd are filtered hydrogen film section 20c leach the methanation of carbon monoxide in product.
In one embodiment, above-mentioned Diaphragm type hydrocarbon recombination hydrogen production device 50 is the cylindric of two different diameters wide at the top and narrow at the bottom, but, the present invention is not limited thereto, the shape of Diaphragm type hydrocarbon recombination hydrogen production device 50 and the configuration in each district can according to reality need make any change and change.
Please refer to Fig. 5, the top of Diaphragm type hydrocarbon recombination hydrogen production device 50 has opening for feed 19, charging enters among Diaphragm type hydrocarbon recombination hydrogen production device 50 by opening for feed 19, after heating via the 4th heat exchanger 16d in the 600a of preheating zone, main heat exchanger 14 can be sent into via feed-pipe 21, after the hot fluid heats in main heat exchanger 14, then discharge via the outlet 22 of main heat exchanger 14, enter the first restructuring section 18a of recombination zone 400 from entrance 23.
Please refer to Fig. 5, charging is carried out restructuring generation first at the first restructuring section 18a and to be recombinated atmosphere, and first recombinates atmosphere by exporting 24 discharges, enters main heat exchanger 14 again via runner.First restructuring atmosphere cools via the cold fluid of main heat exchanger 14.Through the first restructuring atmosphere of cooling, enter the first filter hydrogen film section 20a via runner by entrance 36 and filter.First filter hydrogen film section 20a filters the first product (being such as hydrogen) of being formed after methanation section 15 methanation, then is discharged by outlet 39.The first residual air left by first filter hydrogen film section 20a filters then is discharged via outlet 38, then via runner, by being positioned at preheating zone 600b, after the second heat exchanger 16b heats, enters the second restructuring section 18b by entrance 28.
Please refer to Fig. 5 and Fig. 8, the first residual air is through the second restructuring section 18b restructuring, and its second restructuring atmosphere produced is by after exporting 30 discharges, and via runner, then enter main heat exchanger 14, the cold fluid via main heat exchanger 14 cools.Through the second restructuring atmosphere of cooling, enter the second filter hydrogen film section 20b again via runner and filter.Second filter hydrogen film section 20b filters the second product (being such as hydrogen) of being formed after methanation section 15 methanation, then is discharged by outlet 39.The second residual air left by second filter hydrogen film section 20b filters then is discharged via outlet 40, then via runner, by being positioned at preheating zone 600b, after the 3rd heat exchanger 16c heats, enters the 3rd restructuring section 18c by entrance 32.
Second residual air is through the second restructuring section 18b restructuring, and its 3rd restructuring atmosphere produced by after exporting 34 discharges, then enters main heat exchanger 14 via runner, then cools via the cold fluid of main heat exchanger 14.Through the 3rd restructuring atmosphere of cooling, then enter the 3rd filter hydrogen film section 20c via runner and filter.3rd filter hydrogen film section 20c filters the third product (being such as hydrogen) that formed after methanation section 15 methanation, then is discharged by outlet 39.The 3rd left residual air then can be discharged outside reformer, or passes among combustion chamber 12 again.
With the Diaphragm type hydrocarbon recombination hydrogen production device of above-mentioned Fig. 5, its volume is 24 liters, and filter hydrogen film section is made up of the palladium film pipe of 30, provides power density to be that the power of 76 watts/liter is tested.In an experiment, measure the first restructuring section 18a center part (A1) of Diaphragm type hydrocarbon recombination hydrogen production device, the second restructuring section 18b bottom (A2), the 3rd restructuring section 18c bottom (A3), the 3rd restructuring section 18c top (A4), the first filter hydrogen film section 20a top (B1), the first filter hydrogen film section 20a bottom (B4), the second filter hydrogen film section 20b top (B2), the second filter hydrogen film section 20b bottom (B3), the temperature distribution situation in its each district is as shown in table 1.
Table 1
Show the temperature of recombination zone all at more than 500 degree Celsius by the result of table 1, be conducive to the carrying out of recombining reaction.The temperature of thin film region, then between 300 degree to 424 degree Celsius, can maintain the strainability of palladium filter hydrogen film.
Hydrogen rate that example 1 to 12 is on average produced is 1.1Nm
3/ hour, hydrogen purity is 98%, and the concentration of carbon monoxide is less than 10ppm.
To sum up above-mentioned, thin film region and recombination zone are separated by Diaphragm type hydrocarbon recombination hydrogen production device of the present invention, only transmitting runner makes fluid circulate, and restructuring atmosphere enter the filter hydrogen film section of thin film region before all have to pass through main heat exchanger, main heat exchanger is utilized to carry out the control of temperature, enter filter hydrogen film section after making the cooling of restructuring atmosphere again, therefore, be conducive to the life-span of safeguarding filter hydrogen film.
Moreover, due to charging enter restructuring section before all through over-heat-exchanger, heat exchanger can be utilized to carry out the control of temperature, makes the temperature increase of charging, reach the service temperature of recombining reaction of the section that is suitable for recombinating.
In addition, Diaphragm type hydrocarbon recombination hydrogen production device of the present invention contains the restructuring section-filter hydrogen film section of more than two sections, therefore, effectively can promote transformation efficiency, promote and produce hydrogen rate, and the hydrogen purity of institute's output be high, the concentration of carbon monoxide is low, can be directly fuel cell for proton exchange membrane.
Although the present invention is with embodiment openly as above, so itself and be not used to limit the present invention, without departing from the spirit and scope of the present invention, when doing a little change and retouching, therefore protection scope of the present invention is as the criterion with claims any those skilled in the art.
Claims (18)
1. a film type hydrocarbon polymer reformation hydrogen-producing machine, comprising:
First reforming sections, in order to catalytic reforming feedstock, to form the first reformation atmosphere;
First filter hydrogen film section, connects described first reforming sections, in order to filter described first reformation atmosphere, forms the first product and the first residual air;
Second reforming sections, connects described first filter hydrogen film section, in order to described first residual air of reforming, to form the second reformation atmosphere;
Second filter hydrogen film section, connects described second reforming sections, in order to filter described second reformation atmosphere, forms the second product and the second residual air; And
Main heat exchanger, connect described first reforming sections and described first and filter hydrogen film section, and connect described second reforming sections and described second and filter hydrogen film section, described main heat exchanger provides hot-fluid and cold fluid, described cold fluid, in order to before enter described first filter hydrogen film section and described second filter hydrogen film section respectively in described first reformation atmosphere and described second reformation atmosphere, cools described first reformation atmosphere and described second reformation atmosphere;
First heat exchanger, is connected with described first reforming sections, in order to heat described charging; And
Second heat exchanger, filters hydrogen film section with described first and described second reforming sections is connected, and in order to receive described first residual air, heats before described first residual air flows into described second reforming sections;
Combustion zone, is provided with a combustion chamber, and described combustion chamber, in order to combustion fuel and air, is at least connected with described first heat exchanger and described second heat exchanger.
2. film type hydrocarbon polymer reformation hydrogen-producing machine as claimed in claim 1, is characterized in that, before described charging enters described first heat exchanger, first by described main heat exchanger, with the described hot fluid heats through described main heat exchanger.
3. film type hydrocarbon polymer reformation hydrogen-producing machine as claimed in claim 1, is characterized in that, more comprise:
Tri-reforming section, in order to described second residual air of reforming, to form tri-reforming atmosphere;
3rd filter hydrogen film section, in order to filter described tri-reforming atmosphere, forms third product and the 3rd residual air;
3rd heat exchanger, filters hydrogen film section with described second and described tri-reforming section is connected, and in order to receive described second residual air, heats before described second residual air flows into described tri-reforming section, and
Described tri-reforming atmosphere, before entering described 3rd filter hydrogen film section, is introduced into described main heat exchanger, with the described tri-reforming atmosphere of described cold fluid cooling.
4. film type hydrocarbon polymer reformation hydrogen-producing machine as claimed in claim 3, it is characterized in that, described first reforming sections and described first is filtered between hydrogen film section separate, separate between described first filter hydrogen film section and described second reforming sections, described second reforming sections and described second is filtered between hydrogen film section separate, separate between described second filter hydrogen film section and described tri-reforming section, described tri-reforming section and the described 3rd is filtered between hydrogen film section separate, and respectively with flow passage.
5. film type hydrocarbon polymer reformation hydrogen-producing machine as claimed in claim 3, before wherein said charging enters described first heat exchanger, first by described main heat exchanger, with the described hot fluid heats through described main heat exchanger.
6. film type hydrocarbon polymer reformation hydrogen-producing machine as claimed in claim 4, is characterized in that, comprise described charging by the described cold fluid of described main heat exchanger.
7. film type hydrocarbon polymer reformation hydrogen-producing machine as claimed in claim 4, it is characterized in that, comprise the described first reformation atmosphere flowed out from described first reforming sections, the described second reformation atmosphere flowed out from described second reforming sections, the described tri-reforming atmosphere that flows out from described tri-reforming section by the described hot-fluid of described main heat exchanger, and carry out heat exchange by the described hot-fluid of described main heat exchanger and described charging.
8. film type hydrocarbon polymer reformation hydrogen-producing machine as claimed in claim 3, is characterized in that, comprising:
Main heat exchange zone, described main heat exchanger is arranged in described heat exchange zone;
Methanation region, is positioned at above described main heat exchange zone, or filters hydrogen film section, described second and filter the outlet that hydrogen film section and the described 3rd filters hydrogen film section product with described first and be connected;
Thin film region, described first filter hydrogen film section, described second filter hydrogen film section and the described 3rd are filtered hydrogen film section and are arranged in described thin film region;
Reformer section, is surrounded on the top or around of described combustion zone, described first reforming sections, described second reforming sections and described tri-reforming section, is separately arranged in described reformer section; And
Preheating zone, be positioned at outside the fluid outlet of periphery, described reformer section and described methanation region, described first heat exchanger, the second heat exchanger and described 3rd heat exchanger are arranged in the described preheating zone of periphery, described reformer section.
9. film type hydrocarbon polymer reformation hydrogen-producing machine as claimed in claim 8, is characterized in that, described 3rd residual air produced by described 3rd filter hydrogen film section is back to described combustion chamber.
10. film type hydrocarbon polymer reformation hydrogen-producing machine as claimed in claim 8, is characterized in that, more comprise the 4th heat exchanger, be arranged in the described preheating zone of described methanation region fluid outlet.
11. film type hydrocarbon polymer reformation hydrogen-producing machines as claimed in claim 10, it is characterized in that, the burning gas that described second product that the hot-fluid of described 4th heat exchanger comprises described first product that described first filter hydrogen film section formed, described second filter hydrogen film section is formed or the described third product that described 3rd filter hydrogen film section is formed, combustion chamber produce, the cold fluid of described 4th heat exchanger comprises described charging, the air of burning and fuel.
12. film type hydrocarbon polymer reformation hydrogen-producing machines as claimed in claim 1, it is characterized in that, more comprise the 4th heat exchanger, the burning gas that described second product that the hot-fluid of described 4th heat exchanger comprises described first product that described first filter hydrogen film section formed, described second filter hydrogen film section is formed, combustion chamber produce, the cold fluid of described 4th heat exchanger comprises described charging, the air of burning and fuel.
13. 1 kinds of film type hydrocarbon polymer reformation hydrogen-producing machines, comprising:
First reforming sections, in order to catalytic reforming feedstock, to form the first reformation atmosphere;
First filter hydrogen film section, in order to filter described first reformation atmosphere, forms the first product and the first residual air;
Second reforming sections, in order to described first residual air of reforming, to form the second reformation atmosphere;
Second filter hydrogen film section, in order to filter described second reformation atmosphere, forms the second product and the second residual air;
First heat exchanger, is connected with described first reforming sections, in order to heat described charging; And
Second heat exchanger, filters hydrogen film section with described first and described second reforming sections is connected, and in order to receive described first residual air, heats before described first residual air flows into described second reforming sections;
Combustion zone, is provided with combustion chamber, and described combustion chamber, in order to combustion fuel and air, is at least connected with described first heat exchanger and described second heat exchanger;
Preheating zone, be positioned at outside the fluid outlet of periphery, reformer section and methanation region, described first heat exchanger, the second heat exchanger are arranged in the described preheating zone of periphery, described reformer section;
4th heat exchanger, the burning gas that the hot-fluid of described 4th heat exchanger comprises described first product that described first filter hydrogen film section produces, described second product that described second filter hydrogen film section produces, described combustion chamber produce, the cold fluid of described 4th heat exchanger comprises described charging, the air of burning and fuel;
Described first reforming sections and described first is filtered between hydrogen film section separate, and separate between described first filter hydrogen film section and described second reforming sections, described second reforming sections and described second is filtered between hydrogen film section separate.
14. film type hydrocarbon polymer reformation hydrogen-producing machines as claimed in claim 13, is characterized in that, more comprise:
Tri-reforming section, in order to described second residual air of reforming, to form tri-reforming atmosphere;
3rd filter hydrogen film section, in order to filter described tri-reforming atmosphere, forms third product and the 3rd residual air;
3rd heat exchanger, filters hydrogen film section with described second and described tri-reforming section is connected, and in order to receive described second residual air, heats before described second residual air flows into described tri-reforming section,
Wherein, described 3rd heat exchanger is arranged in described preheating zone, and separate between described second filter hydrogen film section and described tri-reforming section.
15. film type hydrocarbon polymer reformation hydrogen-producing machines as claimed in claim 14, it is characterized in that, described tri-reforming section and the described 3rd is filtered between hydrogen film section separate, and respectively with flow passage.
16. film type hydrocarbon polymer reformation hydrogen-producing machines as claimed in claim 14, it is characterized in that, described first reforming sections is positioned at above described combustion chamber, described second reforming sections and described tri-reforming section are surrounded on around described combustion chamber, and described second heat exchanger and described 3rd heat exchanger are surrounded on described second reforming sections and described tri-reforming section is peripheral.
17. film type hydrocarbon polymer reformation hydrogen-producing machines as claimed in claim 16, is characterized in that, described 3rd residual air produced by described 3rd filter hydrogen film section is back to described combustion chamber.
18. film type hydrocarbon polymer reformation hydrogen-producing machines as claimed in claim 14, is characterized in that, the hot-fluid of described 4th heat exchanger more comprises the described third product that described 3rd filter hydrogen film section produces.
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| TW100149586A TWI464110B (en) | 2011-12-29 | 2011-12-29 | Membrane-based reforming hydrogen generator for hydrocarbons |
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| TW200922870A (en) * | 2007-11-20 | 2009-06-01 | Ind Tech Res Inst | Hydrogen generation system |
| CN101626975A (en) * | 2007-01-09 | 2010-01-13 | 艾奈德有限公司 | Reforming system, method for operating a reforming system and fuel cell system |
| CN102020245A (en) * | 2009-09-16 | 2011-04-20 | 碧氢科技开发股份有限公司 | Hydrogen generator and application thereof |
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| JP3035038B2 (en) * | 1991-11-25 | 2000-04-17 | 三菱重工業株式会社 | Hydrogen production method |
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| US7939051B2 (en) * | 2006-05-23 | 2011-05-10 | Idatech, Llc | Hydrogen-producing fuel processing assemblies, heating assemblies, and methods of operating the same |
| CN101785956B (en) * | 2009-01-24 | 2012-02-29 | 碧氢科技开发股份有限公司 | Membranous tube complex and high-purity hydrogen generating device using same |
| JP2011136868A (en) * | 2009-12-28 | 2011-07-14 | Idemitsu Kosan Co Ltd | Reforming unit and fuel cell system |
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| CN101626975A (en) * | 2007-01-09 | 2010-01-13 | 艾奈德有限公司 | Reforming system, method for operating a reforming system and fuel cell system |
| TW200922870A (en) * | 2007-11-20 | 2009-06-01 | Ind Tech Res Inst | Hydrogen generation system |
| CN102020245A (en) * | 2009-09-16 | 2011-04-20 | 碧氢科技开发股份有限公司 | Hydrogen generator and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI464110B (en) | 2014-12-11 |
| CN103183317A (en) | 2013-07-03 |
| TW201326029A (en) | 2013-07-01 |
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