CN101177240B - Integrated device for preparing hydrogen by the recapitalization of dimethyl ether aqueous vapor and method - Google Patents
Integrated device for preparing hydrogen by the recapitalization of dimethyl ether aqueous vapor and method Download PDFInfo
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- CN101177240B CN101177240B CN2007101770920A CN200710177092A CN101177240B CN 101177240 B CN101177240 B CN 101177240B CN 2007101770920 A CN2007101770920 A CN 2007101770920A CN 200710177092 A CN200710177092 A CN 200710177092A CN 101177240 B CN101177240 B CN 101177240B
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 121
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 121
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 30
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 72
- 238000000629 steam reforming Methods 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 claims abstract description 24
- 238000002485 combustion reaction Methods 0.000 claims abstract description 22
- 238000002407 reforming Methods 0.000 claims abstract description 16
- 239000012528 membrane Substances 0.000 claims abstract description 10
- 229910001316 Ag alloy Inorganic materials 0.000 claims abstract description 9
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 47
- 239000007789 gas Substances 0.000 claims description 47
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- 238000009738 saturating Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 10
- 229910000510 noble metal Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 239000011973 solid acid Substances 0.000 claims description 8
- 238000000429 assembly Methods 0.000 claims description 7
- 230000000712 assembly Effects 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000006057 reforming reaction Methods 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000008878 coupling Effects 0.000 abstract description 6
- 238000010168 coupling process Methods 0.000 abstract description 6
- 238000005859 coupling reaction Methods 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000446 fuel Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000003915 liquefied petroleum gas Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
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- 238000003860 storage Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910002668 Pd-Cu Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- -1 hydrogen dimethyl ether Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 230000008016 vaporization Effects 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention discloses an integrated dimethyl ether steam reforming hydrogen-production device and a method, belonging to the hydrogen-production equipment and the method. The invention utilizes a dual-jacketed membrane reactor to realize the coupling of an exothermic reaction and an endothermic reaction and the coupling of a catalytic reaction and a product separation. The invention is characterized in that the central tube of the double cannula is a hydrogen permeation membrane made of palladium silver alloy for in-situ separation of H2, the product of the reaction system; two reforming catalysts are filled in a jacket of the double cannula and the dimethyl ether steam reforming hydrogen production is carried out in the jacket of the tube side; a combustion supporting catalyst is filledin the shell side out of the double cannula to supply heat for the dimethyl ether steam reforming reaction. The invention has the advantages of greatly promoting the steam reforming reaction rate ofthe dimethyl ether, the heat utilization rate and the product purity. The invention obtains high purity hydrogen at lower reaction temperature and pressure, in which the conversion of dimethyl ether canreach 80%, the hydrogen recovery rate 85%, the hydrogen production rate 0.05 to 0.6 m<3>/h, the hydrogen purity 99.5% and the thermal efficiency of the system is above 80%.
Description
Technical field
The present invention relates to a kind of is the device and method that raw material is produced hydrogen with the dme, particularly a kind of integrated form dimethyl ether-steam reforming device for producing hydrogen and method.
Background technology
Hydrogen Energy is with its cleaning, efficient, the renewable the most potential energy in this century that is regarded as, and it still is the low pollution of a kind of ideal or the zero automobile-used energy that pollutes at present.At present, become one of hot subject of current fuel cell field based on the research and development of liquid hydrocarbon (as methyl alcohol) the mobile hydrogen making process of chemical process.With methyl alcohol is that fuel can solve problems such as storage and transportation, but the methyl alcohol specific energy density is still undesirable, and toxicity is bigger, in case leakage is all very big to the harm of human body and environment, in addition, the used Infrastructure of annotating also need rebulid.
In recent years dimethyl ether-steam reforming hydrogen manufacturing (DME SR) research of process has been caused investigator's concern, dme is a kind of high-energy-density hydrogen carrier of cleaning, very easily be compressed into liquid (0.5MPa), physical properties is similar to liquefied petroleum gas (LPG) (LPG), have hydrogen content height, calorific value height, be easy to advantages such as storage, transportation, the discharge after its burning is far smaller than existing various fuel to the pollution of environment.Compare with other hydrogen production process, dme has advantages such as raw material is easy to get, hydrogen richness height, accumulating convenience, hydrogen manufacturing mild condition, is applicable to mobile hydrogen making.
Dme and water vapor be reformation hydrogen production under catalyst action, and its reaction formula is as follows:
CH
3OCH
3+H
2O＝2CH
3OH ΔH
298＝+37kJ/mol (1)
CH
3OH+H
2O＝3H
2+CO
2 ΔH
298＝+49kJ/mol (2)
Total reaction is:
CH
3OCH
3+3H
2O＝6H
2+2CO
2ΔH
298＝+135kJ/mol (3)
The hydrogen content height that the dimethyl ether-steam reforming hydrogen production reaction obtains, and reaction conditions gentleness, weak point is that the dimethyl ether-steam reforming reaction is a strong endothermic reaction, and the vaporization of reaction itself and raw water all need be absorbed heat, and needs the heat supply of combustion parts fuel during hydrogen manufacturing.
Japanese Patent (clear 63-295402) has proposed to produce the method for hydrogen with sintered glass-Pd-Cu composite film reactor, this method adopts membrane reactor, reaction one is separated carry out synchronously, has broken Equilibrium limit, transformation efficiency is improved, but this method adopts higher service temperature, the energy consumption height for obtaining high hydrogen productive rate, and this method gas production rate is low, direct products are gas mixtures of hydrogen and argon, rather than pure hydrogen, are difficult to separate.Method and system about the dme steam reformation has relevant patent, as CN1126709C, and CN1044896C and CN1123530C etc.Patent CN1126709C, CN1044896C propose in the method that dimethyl ether catalysis hydrogen manufacturing under the steam situation is arranged, this patent make dme at first hydrolysis produce contain hydrocarbon and hydrogen mixture after, also will carry out the aqueous vapor reacting condition to reaction product makes a large amount of carbon monoxide change into carbonic acid gas, and be rich in carbon monoxide in the product, thereby make dme hydrogen manufacturing flow process complexity, energy consumption is higher; Though patent CN1123530C proposes to be rich in the method for hydrogen and with hydrogen partial oxidation heat supply with the generation of steam reformation dme, but this patent is preferably used fluidized-bed reactor, operation pressure is higher, gaseous fraction complexity in the reaction product, be difficult to obtain the hydrogen of higher degree, above-mentioned patent all is not suitable for mobile hydrogen making or small-sized hydrogen source hydrogen manufacturing.Therefore, be necessary to design a kind of rational structure more, give full play to the characteristics of the dme energy and the advantage of dme hydrogen manufacturing, realize that dimethyl ether-steam reforming hydrogen manufacturing is applicable to mobile hydrogen making or small-sized hydrogen source hydrogen manufacturing.
Summary of the invention
At the deficiencies in the prior art and defective, the present invention proposes a kind of integrated form dimethyl ether-steam reforming device for producing hydrogen and method, make this invention with being integral of unit design such as fuel heat supply, steam reforming reaction and hydrogen-rich gas isolation of purified, realize thermopositive reaction and the coupling of thermo-negative reaction and the coupling of catalyzed reaction and product sepn process, under lower temperature of reaction and pressure, obtain highly purified hydrogen, to be applicable to mobile hydrogen making or small-sized hydrogen source hydrogen manufacturing.
Technical scheme of the present invention is as follows:
A kind of integrated form dimethyl ether-steam reforming device for producing hydrogen, it is characterized in that: this device contains reactor body, the two saturating hydrogen assemblies of sleeve pipe of many groups evenly are set in reactor body, every group of two saturating hydrogen assemblies of sleeve pipe are made up of pipe core and outer tube, described pipe core adopts palladium alloy membrane or composite palladium film, filling reforming catalyst in two sleeve pipe chucks, the interior filling of the shell side combustion supporting catalyst that two sleeve pipes are outer, the telescopic bottom is provided with the porous end cap that reforming reaction tail gas is seen through outside; Be provided with outlet of dispensing gas and unstripped gas inlet on reactor top successively, be provided with hydrogen outlet in reactor head; Bottom at reactor is provided with portfire, and the bottom of reactor is respectively equipped with the overside port of gas inlet and catalyzer.
Described pipe core adopts the palladium-silver alloy film, and the palladium in the palladium-silver alloy film is 2.3～9: 1 with the mass percent of silver.Be preferably 3: 1.
The present invention also provides a kind of method that adopts described integrated form dimethyl ether-steam reforming device for producing hydrogen, it is characterized in that this method carries out as follows:
1) enters in two sleeve pipe chucks by the unstripped gas inlet after water and dme mix, in two sleeve pipe chucks, flow from top to bottom, the dimethyl ether-steam reforming reaction takes place under the effect of reforming catalyst, and the reforming reaction temperature is 200～300 ℃, and reaction pressure is 0.1～0.5MPa; The compound dual-function catalyst that reforming catalyst adopts solid acid and metal catalyst to form, the weight ratio of solid acid and metal catalyst is 1: 5～5: 1;
2) after the two saturating hydrogen components apart of sleeve pipe of hydrogen process that the dimethyl ether-steam reforming reaction obtains, enter reactor top, discharge from the hydrogen outlet of reactor head by pipe core; The tail gas and the unsegregated hydrogen of dimethyl ether-steam reforming reaction enter reactor bottom by the porous end cap; Pressure in the described pipe core is normal pressure;
3) enter reaction end gas and the unsegregated hydrogen and the air mixed of reactor bottom, after the portfire heating, under the effect of combustion supporting catalyst, progressively from bottom to top burning is that dimethyl ether-steam reforming reacts heat supply in the shell side two sleeve pipes outside; Combustion reactions tail gas is discharged reactor from the outlet of dispensing gas; Described combustion supporting catalyst adopts loaded noble metal catalyst.
In the aforesaid method, reforming catalyst preferably adopts the mixture of molecular sieve catalyst ZSM-5 and copper-based catalysts, and the weight ratio of molecular sieve ZSM-5 and copper-based catalysts is 1: 2～2: 1.Described combustion supporting catalyst preferably adopts Pd/Al
2O
3Noble metal catalyst.
The present invention compared with prior art, have the following advantages and the high-lighting effect: this invention utilizes palladium alloy membrane or the composite palladium film selection perviousness to hydrogen, in time the hydrogen that the dimethyl ether-steam reforming reaction is generated shifts out from product, thereby the raising reaction conversion ratio obtains highly purified hydrogen simultaneously under lower temperature of reaction and pressure; Utilize dual-function catalyst that dme hydrolysis reaction and methanol steam reforming reaction are coupled together, improve the transformation efficiency and the hydrogen yield of dme; Utilize electrical heating wire that reactant is preheating to initial reaction temperature, after the dimethyl ether-steam reforming reaction beginning, unreacted dme, unsegregated hydrogen in the reaction end gas are burnt,, make full use of the energy for the reaction heat supply; This device is realized thermopositive reaction and the coupling of thermo-negative reaction and the coupling of catalyzed reaction and product sepn process with being integral of unit design such as fuel heat supply, steam reforming reaction and hydrogen-rich gas isolation of purified.
Description of drawings
Fig. 1 is the typical structure synoptic diagram of dimethyl ether-steam reforming device for producing hydrogen.
Fig. 2 is a dimethyl ether-steam reforming hydrogen manufacturing schema.
Among the figure: 1. gas inlet; 2. end socket; 3. porous end cap; 4. cylindrical shell; 5. combustion supporting catalyst; 6. reforming catalyst; 7. dispensing gas outlet; 8. unstripped gas enters the mouth; 9. hydrogen outlet; 10. saturating hydrogen pipe card; 11. porous card; 12. outer tube card; 13. pipe core; 14. outer tube; 15. support flower stand; 16. air-distributor; 17. catalyst loading and unloading mouth; 18. portfire; 19. gas of dimethyl ether steel cylinder; 20. pump; 21. air gas steel cylinder; 22. reducing valve; 23. mass flowmeter; 24. reactor; 25. thermostat container; 26. cold-trap; 27. liquid collecting jar; 28. back pressure valve; 29. wet flow indicator; 30. gas chromatograph; 31. master control system.
Embodiment
In conjunction with the accompanying drawings structure of the present invention, principle and technological process are further described.
Fig. 1 is the typical structure synoptic diagram of dimethyl ether-steam reforming device for producing hydrogen.This device contains reactor body, and the two saturating hydrogen assemblies of sleeve pipe of many groups evenly are set in reactor body, and every group of two saturating hydrogen assemblies of sleeve pipe are made up of pipe core 13 and outer tube 14, are provided with the porous end cap 3 that reforming reaction tail gas is seen through in the bottom of outer tube 14; Pipe core adopts palladium alloy membrane or composite palladium film, and the pipe core inwall constitutes the infiltration chamber, is used for the product H of original position separating reaction system
2Filling dimethyl ether-steam reforming catalyzer 6 carries out the reaction of dme reformation catalyzing manufacturing of hydrogen in two sleeve pipe chucks in two sleeve pipe chucks; The interior filling of the shell side combustion supporting catalyst 5 that two sleeve pipes are outer is used for catalyticcombustion dimethyl ether-steam reforming reaction end gas and unsegregated hydrogen; Be provided with outlet 7 of dispensing gas and unstripped gas inlet 8 successively on reactor top.Be provided with hydrogen outlet 9 in reactor head, the hydrogen of dimethyl ether-steam reforming Reaction Separation is discharged reactor from hydrogen outlet 9.Be provided with portfire 18 in the bottom of reactor, be used for heating fuel.The bottom of reactor is respectively equipped with the overside port 17 of gas inlet 1 and catalyzer, and gas inlet 1 is the passage of logical people's air in the reactor, and the overside port 17 of catalyzer is the passage of loading and unloading catalyzer.
The unstripped gas dme enters in two sleeve pipe chucks from the unstripped gas inlet 8 on reactor top, dme flows in two sleeve pipe chucks from top to bottom, enter reactor bottom from porous end cap 3, air enters reactor bottom by gas inlet 1, portfire 18 adds the gas mixture of warm air and dme, the outer interior combustion supporting catalyst 5 of shell side of two sleeve pipes adopts loaded noble metal catalyst, preferably Pd/Al
2O
3Noble metal catalyst, what of combustion supporting catalyst loadings can be decided according to the actual requirements.Under the effect of combustion supporting catalyst 5, progressively from bottom to top the burning of dme and the air shell side outside two sleeve pipes, the shell side of heat outside two sleeve pipes passes in two sleeve pipe chucks, and the interior temperature of two sleeve pipe chucks is raise gradually, and combustion reactions tail gas is discharged reactor from dispensing gas outlet 7.When the temperature in two sleeve pipe chucks is elevated to the dimethyl ether-steam reforming temperature of reaction, ejector priming 20, enter in two sleeve pipe chucks by unstripped gas inlet 8 behind water and the dme uniform mixing, the dimethyl ether-steam reforming reaction takes place under the effect of reforming catalyst 6, the compound dual-function catalyst that the dimethyl ether-steam reforming catalyzer adopts solid acid and metal catalyst to form, the weight ratio of solid acid and metal catalyst is 1: 5～5: 1; Be preferably the catalyzer of molecular sieve catalyst ZSM-5 and copper-based catalysts physical mixed, molecular sieve catalyst ZSM-5 and the weight ratio of copper-based catalysts are that the part by weight between 1: 2～2: 1 combines, and what of reforming catalyst loadings can be decided according to the actual requirements.Raw water and dme mol ratio are 3: 1～6: 1, and temperature of reaction is 200 ℃～300 ℃, and reaction pressure is 0.1～0.5MPa, and saturating hydrogen pipe assembly internal pressure is a normal pressure.The hydrogen that the dimethyl ether-steam reforming reaction obtains enters reactor top through after the saturating hydrogen components apart by pipe core 13, discharge pipe core assembly 13 pipe ranges 100～300mm, caliber 10～20mm from the hydrogen outlet 9 of reactor head, thickness 0.06mm produces hydrogen scale 0.02～0.3m
3/ h.Dimethyl ether-steam reforming reaction end gas and unsegregated hydrogen enter reactor bottom by porous end cap 3, with the air mixed afterfire be dimethyl ether-steam reforming reaction heat supply, to keep the required heat of dimethyl ether-steam reforming reaction, keep the temperature of reaction of dimethyl ether-steam reforming part constant, dme reforming reactants and fuel adverse current flow, the heat transfer efficiency height.Simultaneously can be according to the demand of actual hydrogen output, by the scantlings of the structure of the two saturating hydrogen assemblies of sleeve pipe of the corresponding adjustment of this structure and the loadings of catalyzer.
The outlet of reactor is a thermostat container 25, keeps higher temperature so that all reactants and product continue to keep gaseous phase, is provided with resistant to elevated temperatures six-way valve in the thermostat container, can the online acquisition reactor outlet gas enters chromatogram and carries out proximate analysis.Tail gas carries out gas-liquid separation from entering cold-trap 26 after thermostat container comes out, gas phase is kept to normal pressure through behind the back pressure valve 28, is measured by wet flow indicator 29, and liquid phase enters liquid collection tank, regularly collect Weighing, the liquid phase composition also adopts gas-chromatography 30 to analyze.Measurement and control process are passed through computer realization with master control system 31.
Calculation formula is as follows:
This shows, integrated form dimethyl ether-steam reforming device for producing hydrogen among the present invention is when carrying out the dimethyl ether-steam reforming reaction, the dimethyl ether-steam reforming reaction end gas is carried out catalyst combustion reaction, be dimethyl ether-steam reforming reaction heat supply, this device does not need extra heat-exchange equipment.In addition, because this reforming system adopts countercurrent flow (heat-transfer medium is opposite with the flow direction of dimethyl ether-steam reforming raw material, and driving force of heat transfer is big), heat transfer efficiency is improved.
The present invention is owing to adopt palladium-silver alloy film pipe, thereby can separate pure hydrogen under 200 ℃～300 ℃ low temperature, and device for producing hydrogen compact construction, miniaturization are easy to carry about with one, and catalyzer is not easy to wear simultaneously, interpolation or more raw catalyst easily.System can realize can be used for small-sized hydrogen source and vehicle-mounted hydrogen production from heat supply.This integrated form dimethyl ether-steam reforming device for producing hydrogen can be handled pluralities of fuel, comprises gasoline, methyl alcohol, ethanol and other hydrocarbon fuel.
Adopt the integrated form dimethyl ether-steam reforming device for producing hydrogen dimethyl ether conversion rate 60%～80% among the present invention, the hydrogen rate of recovery 85%, the purity of hydrogen reaches 99.5%, the product hydrogen scale 0.02～0.3m of reaction
3/ h, system thermal efficiency are 80%.When the hydrogen rate of recovery was 80%, whole dimethyl ether-steam reforming device for producing hydrogen can reach autothermal equilibrium.Temperature of reaction is low, and energy consumption is low, reacts and separates synchronously, and easy to operate, facility investment is few.
Embodiments of the invention are as follows:
Embodiment 1
0.02m
3/ h dme device for producing hydrogen
Make up reaction unit as Fig. 2, adopt membrane reactor, 200 ℃ of temperature of reaction, reaction pressure is 0.1MPa, and pipe core adopts palladium-silver alloy, and palladium is 3: 1 with the mass percent of silver, the pipe core internal pressure is a normal pressure, and the inlet amount of dme is 500ml/min, and the mol ratio of water and dme is 3: 1; Reforming catalyst adopts the mixture of molecular sieve ZSM-5 and copper-based catalysts to be total to 10g, and the weight ratio of molecular sieve catalyst ZSM-5 and copper-based catalysts is 1: 1, and combustion supporting catalyst adopts Pd/Al
2O
3Noble metal catalyst 5g, pipe core assembly pipe range 300mm, caliber 10mm, thickness 0.06mm, pipe core is 5, obtaining the dimethyl ether conversion rate is 60%, produces hydrogen scale 0.02m
3/ h, hydrogen recovery rate 82%, the purity of hydrogen reaches 99.5%, and system thermal efficiency is 80%.
0.03m
3/ h dme device for producing hydrogen
Make up reaction unit as Fig. 2, adopt the membrane reactor of embodiment 1,300 ℃ of temperature of reaction, reaction pressure are 0.1MPa, and pipe core adopts palladium-silver alloy, palladium is that 9: 1 pipe core internal pressures are normal pressure with the mass percent of silver, the inlet amount of dme is 500ml/min, and the mol ratio of water and dme is 3: 1, and reforming catalyst adopts the mixture of molecular sieve catalyst ZSM-5 and copper-based catalysts to be total to 10g, the weight ratio of molecular sieve ZSM-5 and copper-based catalysts is 2: 1, and combustion supporting catalyst adopts Pd/A1
2O
3Noble metal catalyst 5g, pipe core assembly pipe range 300mm, caliber 10mm, thickness 0.06mm, pipe core is 5, obtaining the dimethyl ether conversion rate is 80%, produces hydrogen scale 0.03m
3/ h, hydrogen recovery rate 80%, the purity of hydrogen reaches 99.5%, and system thermal efficiency is 80%.
0.3m
3/ h dme device for producing hydrogen
Make up reaction unit as Fig. 2, adopt the membrane reactor of embodiment 1,300 ℃ of temperature of reaction, reaction pressure is 0.5MPa, pipe core adopts the composite palladium film, and the pipe core internal pressure is a normal pressure, and the inlet amount of dme is 5000ml/min, the mol ratio of water and dme is 6: 1, and catalyzer is for adopting solid acid Al
2O
3Be total to 100g, solid acid Al with the mixture of precious metals platinum catalyst
2O
3With the weight ratio of precious metals platinum catalyst be 5: 1, combustion supporting catalyst adopts Pd/Al
2O
3Noble metal catalyst 50g, pipe core assembly pipe range 300mm, caliber 20mm, thickness 0.01mm, pipe core is 15, obtaining the dimethyl ether conversion rate is 80%, produces hydrogen scale 0.3m
3/ h, hydrogen recovery rate 83%, the purity of hydrogen reaches 99.5%, and system thermal efficiency is 85%.
Claims (6)
1. integrated form dimethyl ether-steam reforming device for producing hydrogen, it is characterized in that: this device contains reactor body, the two saturating hydrogen assemblies of sleeve pipe of many groups evenly are set in reactor body, every group of two saturating hydrogen assemblies of sleeve pipe are made up of pipe core (13) and outer tube (14), described pipe core adopts palladium alloy membrane or composite palladium film, filling reforming catalyst (6) in two sleeve pipe chucks, the interior filling of the shell side combustion supporting catalyst (5) that two sleeve pipes are outer is provided with the porous end cap (3) that reforming reaction tail gas is seen through in the bottom of outer tube (14); Be provided with dispensing gas outlet (7) and unstripped gas inlet (8) successively on reactor top, be provided with hydrogen outlet (9) in reactor head; Be provided with portfire (18) in the bottom of reactor, the bottom of reactor is respectively equipped with the overside port (17) of gas inlet (1) and catalyzer.
2. according to the described integrated form dimethyl ether-steam reforming of claim 1 device for producing hydrogen, it is characterized in that: described pipe core adopts the palladium-silver alloy film, and the palladium in the palladium-silver alloy film is 2.3～9: 1 with the mass percent of silver.
3. according to the described integrated form dimethyl ether-steam reforming of claim 2 device for producing hydrogen, it is characterized in that: the palladium in the described palladium-silver alloy film is 3: 1 with the mass percent of silver.
4. the method for the employing integrated form dimethyl ether-steam reforming hydrogen manufacturing of installing according to claim 1 is characterized in that this method carries out as follows:
1) enters in two sleeve pipe chucks by unstripped gas inlet (8) after water and dme mix, in two sleeve pipe chucks, flow from top to bottom, the dimethyl ether-steam reforming reaction takes place under the effect of reforming catalyst, and the reforming reaction temperature is 200～300 ℃, and reaction pressure is 0.1～0.5MPa; The compound dual-function catalyst that reforming catalyst adopts solid acid and metal catalyst to form, the weight ratio of solid acid and metal catalyst is 1: 5～5: 1; Reforming catalyst adopts the mixture of molecular sieve ZSM-5 and copper-based catalysts;
2) after the two saturating hydrogen components apart of sleeve pipe of hydrogen process that the dimethyl ether-steam reforming reaction obtains, enter reactor top, discharge from the hydrogen outlet (9) of reactor head by pipe core (13); The tail gas and the unsegregated hydrogen of dimethyl ether-steam reforming reaction enter reactor bottom by porous end cap (3); Pressure in the described pipe core is normal pressure;
3) enter reaction end gas and the unsegregated hydrogen and the air mixed of reactor bottom, after portfire (18) heating, under the effect of combustion supporting catalyst (5), progressively from bottom to top burning in the shell side outside two sleeve pipes is dimethyl ether-steam reforming reaction heat supply; Combustion reactions tail gas is discharged reactor from dispensing gas outlet (7); Described combustion supporting catalyst adopts loaded noble metal catalyst.
5. according to the method for the described integrated form dimethyl ether-steam reforming of claim 4 hydrogen manufacturing, it is characterized in that: the weight ratio of molecular sieve catalyst ZSM-5 and copper-based catalysts is 1: 2～2: 1.
6. according to the method for the described integrated form dimethyl ether-steam reforming of claim 4 hydrogen manufacturing, it is characterized in that: described combustion supporting catalyst is Pd/Al
2O
3Noble metal catalyst.
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| NL2006245C2 (en) * | 2011-02-18 | 2012-08-21 | Stichting Energie | MEMBRANE REACTOR AND PROCESS FOR THE PRODUCTION OF A GASEOUS PRODUCT WITH SUCH REACTOR. |
| CN102688728A (en) * | 2011-03-21 | 2012-09-26 | 辽宁强森制筛有限公司 | Center tube of reforming reactor without vertical seams |
| CN112299368B (en) * | 2019-07-26 | 2024-04-05 | 青岛海通新材料科技发展有限公司 | High-efficiency hydrogen production catalytic reaction furnace |
| EP4025333A1 (en) | 2019-09-03 | 2022-07-13 | Haldor Topsøe A/S | Reformer furnace with supported reformer tubes |
| CN110683512A (en) * | 2019-10-23 | 2020-01-14 | 张家港氢云新能源研究院有限公司 | Reaction material input mechanism matched with integrated reforming hydrogen production device |
| CN111017874B (en) * | 2019-12-27 | 2020-11-10 | 北京东方华氢科技有限公司 | Fluid preparation system |
| CN111661818B (en) * | 2020-05-15 | 2024-09-27 | 华南理工大学 | Integrated hydrocarbon autothermal reforming hydrogen production reactor |
| CN112263895B (en) * | 2020-09-30 | 2022-05-31 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Palladium/palladium alloy membrane purifier and using method thereof |
| CN214299273U (en) * | 2020-12-10 | 2021-09-28 | 洛阳沃达节能科技有限公司 | Hydrogen production pipe of hydrogen production device and hydrogen production device |
| CN114832739B (en) * | 2022-03-29 | 2023-03-07 | 清华大学 | Coupling fluidized bed device and application thereof |
| WO2024076510A1 (en) * | 2022-10-04 | 2024-04-11 | Oberon Fuels, Inc. | Reactor for converting dimethyl ether to hydrogen |
| CN116395636A (en) * | 2023-03-23 | 2023-07-07 | 上海工程技术大学 | Spiral heating tube type dimethyl ether reforming hydrogen production reactor and application thereof |
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