CN109956450A - A kind of instant hydrogen generating system of methanol-water and its hydrogen production process - Google Patents
A kind of instant hydrogen generating system of methanol-water and its hydrogen production process Download PDFInfo
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- CN109956450A CN109956450A CN201910361470.3A CN201910361470A CN109956450A CN 109956450 A CN109956450 A CN 109956450A CN 201910361470 A CN201910361470 A CN 201910361470A CN 109956450 A CN109956450 A CN 109956450A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 434
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 434
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 389
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 88
- 238000010438 heat treatment Methods 0.000 claims abstract description 88
- 238000000926 separation method Methods 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 239000002994 raw material Substances 0.000 claims abstract description 49
- 239000007788 liquid Substances 0.000 claims abstract description 47
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 278
- 239000007789 gas Substances 0.000 claims description 155
- 230000005540 biological transmission Effects 0.000 claims description 71
- 238000002485 combustion reaction Methods 0.000 claims description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 150000002431 hydrogen Chemical class 0.000 claims description 49
- 238000003860 storage Methods 0.000 claims description 41
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 20
- 239000001569 carbon dioxide Substances 0.000 claims description 20
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 20
- 239000012528 membrane Substances 0.000 claims description 14
- 238000013021 overheating Methods 0.000 claims description 13
- 238000002309 gasification Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000012423 maintenance Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 2
- 239000000446 fuel Substances 0.000 abstract description 15
- -1 liquid container Chemical compound 0.000 abstract description 3
- 235000019441 ethanol Nutrition 0.000 description 26
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 229910052593 corundum Inorganic materials 0.000 description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000012774 insulation material Substances 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 230000006872 improvement Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 239000011490 mineral wool Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 210000004209 hair Anatomy 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
- C01B2203/0822—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel the fuel containing hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0855—Methods of heating the process for making hydrogen or synthesis gas by electromagnetic heating
Abstract
The present invention provides a kind of instant hydrogen generating system of methanol-water, including liquid container, raw material conveying device, hydrogen producer, separation chamber；The hydrogen producer includes evaporator, several reactors and several heaters；The evaporator is built-in with microwave heating equipment；The reactor and heater is cross-linked, and is inside placed with low temperature catalyst for preparing hydrogen or high temperature for hydrogen production catalyst；It further include the pressure buffer device that can control output Hydrogen Vapor Pressure.Invention also provides the hydrogen production process of the instant hydrogen generating system of the methanol-water.Hydrogen generating system and its hydrogen production process starting of the present invention is fast, outlet is stable, loss is low, at low cost, provides practicability significantly, can be applied to vehicle fuel battery.
Description
Technical field
The invention belongs to field of new energy technologies, particularly belong to methanol-water hydrogen producing technology field, in particular to one kind can answer
The instant hydrogen generating system of methanol-water for vehicle fuel battery, and relate to the use of the method that the system prepares hydrogen.
Background technique
Hydrogen fuel cell is the power generator that the chemical energy of hydrogen and oxygen is directly changed into electric energy.The basic principle is that
Hydrogen and oxygen are supplied respectively to anode and cathode by the back reaction of electrolysis water, and hydrogen is reacted by anode to external diffusion and electrolyte
Afterwards, ejected electron reaches cathode by external load.Since hydrogen fuel cell is the electrochemical reaction via utilization hydrogen and oxygen,
Electric current and water are generated, it is not only completely pollution-free, the time-consuming problem of conventional batteries charging is also avoided, is before most developing at present
The new energy mode of scape will significantly mitigate air dirt as can popularizing and applying on vehicle and other high pollution power tools
Dye and greenhouse effects.
Currently, hydrogen fuel cell technology have been relatively mature, it is successfully applied in the fields such as aerospace, automobile, but how
It safely, conveniently prepares, transport, using hydrogen, being the problem of annoying people always.For the problem, it is common practice to
Utilize hydrogen container；However, hydrogen container meets fire and be easy explosion due to having a large amount of hydrogen, hydrogen, safety is not high；In addition, depositing
Storage, the higher cost for conveying hydrogen, reserves are small, bring difficulty for the application of hydrogen gas generation.
" hydrogen " fuel used in hydrogen fuel cell may come from hydrogen caused by the electrolysis of water and any hydrocarbon
Compound, such as natural gas, methanol, ethyl alcohol (alcohol), biogas etc..Preparing hydrogen by reforming methanol be industrial hydrogen production important method it
One, which replaces used hydrogen container using storage methanol-water, solves hydrogen container in hydrogen storage, the fortune various problems such as hydrogen,
Have many advantages, such as that hydrogen-storage density is high, packing storage and transportation is convenient, cheap, no pressure storage, wide market.Conventional methanol weight
Whole hydrogen production process mainly includes vapor reforming hydrogen production, partial oxidation steam reforming and natural reformation hydrogen production, mostly uses hot load greatly
The heating methods such as body circulation heat supply, electric heating or methanol flameless combustion realize thermal energy to catalysis by the heating of wall of reactor
The conduction of oxidant layer and reaction gas, reaction temperature are not easy to control, that there are process conditions is complicated, equipment is huge, heating is uneven,
The problems such as hot spot and cold spot and high energy consumption are easily formed in inside reactor and catalyst layer.
For example, patent of invention ZL201210339913.7 discloses a kind of Methanol water hydrogen production system, which includes liquid
Storage container, heat exchanger, vaporizer, reformer chamber, separation chamber；Liquid container, heat exchanger, vaporizer, reformer chamber, separation chamber
It is sequentially connected by pipeline；It is equipped with ceramic membrane separation device, Metal Palladium membrane separator in separation chamber, first passes through ceramics into separation chamber
Membrane separator pre-processes, and obtains the hydrogen of higher gas purity；The hydrogen of higher degree enters back into Metal Palladium membrane separator,
Obtain the hydrogen of higher purity.The system of stating realizes the hydrogen manufacturing of methanol-water scene, now-making-now-using, without storage.But the system exists
The problem of starting is slow, low efficiency, cold start-up, which generally requires the even time several hours, could start and operate normally, and hydrogen
Whether gas outlet is small and pressure is low, hydrogen production reaction temperature or not, bad practicality.For this purpose, patent of invention ZL201310340475.0
For the slow problem of above-mentioned starting, on the basis of former Methanol water hydrogen production system, this device of solid hydrogen storage container is increased,
In system starting, solid hydrogen is switched to by gaseous hydrogen by gasification module, hydrogen is hydrogen producer by combustion heat release
(reformer chamber) provides starting thermal energy, to further improve hydrogen production efficiency.But since system room to be reformed is warming up to 400 DEG C
Above just to start, there is still a need for or so at least one hour times for starting, while needing to consume a large amount of energy, and persistently right
The heating of reformer chamber catalyst converter continuous high temperature, catalyst attrition is big, can not still be applied to vehicle fuel battery.
Summary of the invention
For existing Methanol water hydrogen production system is slow in the presence of starting speed, reaction temperature is unstable, energy consumption is high, hydrogen gas output
Less and the problems such as pressure is low lead to the defect of bad practicality, the present invention is intended to provide a kind of instant hydrogen manufacturing system of methanol-water
System, while the method that the system prepares hydrogen is provided, which can be applied to vehicle fuel battery.
Specifically, the instant hydrogen generating system of methanol-water of the present invention is achieved through the following technical solutions:
A kind of instant hydrogen generating system of methanol-water, including methanol-water storage container, raw material conveying device, hydrogen producer, separation chamber；Institute
The first alcohol and water of liquid is stored in the methanol-water storage container stated, and is connect by raw material conveying device with hydrogen producer；It is described
Raw material conveying device can realize by the first alcohol and water in methanol-water storage container be delivered to hydrogen producer carry out hydrogen manufacturing；Described
The gas transmission end of separation chamber and hydrogen producer connection, be inside provided with membrane separation device, it can be achieved that hydrogen producer output gas into
Row separation output high-purity hydrogen；
The hydrogen producer includes evaporator, several reactors and several heaters；The reactor and heater
It is cross-linked, catalyst for preparing hydrogen is placed in reactor；
The evaporator is connect with raw material conveying device, reactor respectively, is built-in with microwave heating equipment；The methanol-water
After instant hydrogen generating system starting, microwave heating equipment can convey the liquid methanol come in raw material conveying device immediately and water carries out
Heating and gasifying；
It further include the combustion furnace being connect with hydrogen producer gas transmission end；After the instant hydrogen generating system starting of the methanol-water, combustion furnace
The gas as made from burning hydrogen producer is evaporator, heater is heated.
Evaporator is mainly made of heating room and vaporization chamber two parts.It heats room and provides heat required for evaporation to liquid
Amount, promotes liquid boiling to vaporize；Vaporization chamber is kept completely separate gas-liquid two-phase.The evaporator of hydrogen producer of the present invention is built-in with
Microwave heating equipment (for example, microwave heating pipe), it is relatively conventional to use the external heating side such as combustion furnace by internal microwave heating
Formula, can immediately, quickly to raw material conveying device conveying come in liquid methanol and water carry out heating and gasifying, formed methanol vapor and
Vapor.Hydrogen producer of the present invention is equipped with multiple reactors, is placed with catalyst for preparing hydrogen in reactor, to methanol vapor and
When passing through reactor hydrogen production reaction occurs for vapor, and the methanol vapor not yet reacted completely and vapor can pass through multiple reactions
Device realizes repeatedly reaction, and relatively conventional unique reformer chamber catalyzing manufacturing of hydrogen is compared, and reacts more abundant, more efficient；And system is run
In the process no longer to the catalyst continuous heating in reactor, greatly reduce because being heated at high temperature the loss to catalyst.This hair
The bright hydrogen producer is additionally provided with multiple heaters, and heater is arranged among reactor two-by-two, is cross-linked with reactor, leads to
The combustion heat energy of combustion furnace is crossed to methanol vapor and vapor concurrent heating again after reactor hydrogen production reaction, is made at its temperature
In within the scope of stable optimal reaction temperature, guaranteeing hydrogen production reaction stable operation, hydrogen generating system runs more stable.
The present invention also provides to the further improved technical solution of the instant hydrogen generating system of above-mentioned methanol-water:
A kind of instant hydrogen generating system of methanol-water, including methanol-water storage container, raw material conveying device, hydrogen producer, separation chamber；Institute
The first alcohol and water of liquid is stored in the methanol-water storage container stated, and is connect by raw material conveying device with hydrogen producer；It is described
Raw material conveying device can realize by the first alcohol and water in methanol-water storage container be delivered to hydrogen producer carry out hydrogen manufacturing；Described
The gas transmission end of separation chamber and hydrogen producer connection, be inside provided with membrane separation device, it can be achieved that hydrogen producer output gas into
Row separation output high-purity hydrogen；
The hydrogen producer includes evaporator, several reactors and several heaters；The reactor and heater
It is cross-linked, catalyst for preparing hydrogen is placed in reactor；
The evaporator is connect with raw material conveying device, reactor respectively, is built-in with microwave heating equipment；The methanol-water
After instant hydrogen generating system starting, microwave heating equipment can convey the liquid methanol come in raw material conveying device immediately and water carries out
Heating and gasifying；
It further include the pressure buffer device being connect with separation chamber's gas transmission end, the pressure buffer device is able to achieve to output hydrogen
The control of pressure；
It further include the combustion furnace being connect with hydrogen producer and/or pressure buffer device gas transmission end；The instant hydrogen manufacturing of the methanol-water
System starting after, combustion furnace by burning hydrogen producer and/or pressure buffer device output gas be evaporator, heater into
Row heating.
The more above-mentioned instant hydrogen generating system of methanol-water is compared, and the pressure buffer dress for increasing and connecting with separation chamber's gas transmission end is improved
It sets, which is able to achieve the control to output Hydrogen Vapor Pressure, solves existing hydrogen generating system hydrogen output pressure not
Stable or lower problem.Meanwhile the hydrogen of steady pressure that combustion furnace is exported by combustion pressure buffer unit, it can effectively control
It is made as evaporator, the degree that heater is heated, methanol vapor and vapor is made to be in stable optimal reaction temperature range
It is interior.
As the further improvement of the instant hydrogen generating system of methanol-water of the present invention, the reactor quantity at least two,
The heater quantity at least two.Low temperature catalyst for preparing hydrogen is placed in wherein at least one reactor, remaining is anti-
It answers and is placed with high temperature for hydrogen production catalyst in device.
The starting of existing hydrogen generating system it is slow main reason is that first want heated reformate room reach optimal reaction temperature 400~
570 DEG C, then methanol vapor and vapor progress hydrogen production reaction are conveyed, temperature-rise period just needs or so at least one hour, such as sends out
Methanol water hydrogen production system described in bright patent ZL201310340475.0.It is former after the instant hydrogen generating system starting of methanol-water of the present invention
Material conveying device is that the first alcohol and water of the liquid in methanol-water storage container is delivered to the evaporator of hydrogen producer, in evaporator
If microwave heating equipment heating and gasifying quickly can be carried out to liquid methanol and water, formed 100~350 DEG C methanol vapor and
Vapor.100~350 DEG C of methanol vapor and vapor can react system by being placed with the reactor of low temperature catalyst for preparing hydrogen
Hydrogen, the hydrogen of formation provide operation thermal energy by combustion furnace combustion heat release for hydrogen producer；Persistently overheating is simultaneously finally reached best
The methanol vapor and vapor of reaction temperature gradually with high temperature for hydrogen production catalyst reaction hydrogen, repeatedly, methanol of the present invention
The instant hydrogen generating system of water can rapidly enter good operation circulation.
Low temperature catalyst for preparing hydrogen of the present invention can choose any can realize in low temperature disclosed in the prior art and urge
Change the catalyst of hydrogen manufacturing, such as common CuO/ZnO/ZrO2、CuO/ZnO/Al2O3/ZrO2、CuO/ZnO/CeO2/ZrO2.It is preferred that
CuO/ZnO/CeO2/ZrO2Catalyst.
High temperature for hydrogen production catalyst of the present invention can choose any high temperature for hydrogen production catalyst disclosed in the prior art.
It is preferred that noble metal catalyst and Zn-Cr catalyst, such as Zn-Cr/Al2O3, Pt/Al2O3, Pd/Al2O3, Pt/ZnO/Al2O3, Pd/
ZnO/Al2O3Deng.
Membrane separation device of the present invention can choose any film for being able to achieve Hydrogen Separation disclosed in the prior art
Separator, such as in the film of porous ceramic surface Vacuum Deposition palladium-silver disclosed in patent of invention ZL201310340475.0
Separator, reaction temperature is at 350 DEG C or more.
As the further improvement of the instant hydrogen generating system of methanol-water of the present invention, the reactor is externally provided with insulation material
Material.
Heat-barrier material is equipped with outside reaction chamber can prevent methanol vapor and vapor and reaction chamber cool exterior air from heat occurs
Exchange, causes temperature to decline, to influence reaction effect, also can be reduced heater to the methanol after reactor hydrogen production reaction
The concurrent heating of steam and vapor is lost.
The heat preserving and insulating material is inorganic heat insulation material, such as solid special energy-saving nanometer poromerics, porcelain tendre thermal insulating material
Material, aluminum silicate insulation material, expansion vitrification bead heat-preserving material, glue powder polyphenyl granule insulating material, mineral wool thermal insulation material, rock
Cotton thermal insulation material etc., preferably solid special energy-saving nanometer poromerics, aluminum silicate insulation material, mineral wool thermal insulation material and porcelain tendre heat preservation
Material.
The present invention also provides the hydrogen production process of the instant hydrogen generating system of the methanol-water, specifically includes the following steps:
S1, the starting instant hydrogen generating system of methanol-water, raw material conveying device is by the first alcohol and water of the liquid in methanol-water storage container
It is delivered to the evaporator of hydrogen producer, the microwave heating equipment of evaporator carries out heating and gasifying to the first alcohol and water of liquid immediately,
Formation temperature reaches 100~350 DEG C of methanol vapor and vapor；
S2, temperature reach 100~350 DEG C of methanol vapor and vapor enter be placed with the reactor of low temperature catalyst for preparing hydrogen into
Row reaction hydrogen manufacturing, obtain containing hydrogen, carbon monoxide, carbon dioxide mixed gas A, and from hydrogen producer gas transmission end export；
S3, it is delivered to combustion furnace from the part mixed gas A that hydrogen producer gas transmission end exports, combustion furnace passes through combust mixed gas
It is heated for evaporator, heater, so that the methanol vapor of evaporator gasification and vapor, by reactor but not yet completely
The methanol vapor and vapor of reaction are persistently overheating and finally maintenance temperature is 350~600 DEG C；
S4, the methanol vapor by heating and vapor carry out reaction system into the reactor for being placed with high temperature for hydrogen production catalyst
Hydrogen, obtain containing hydrogen, carbon monoxide, carbon dioxide mixed gas B, and from hydrogen producer gas transmission end export；
S5, combustion furnace, circular flow step S3 are delivered to from the part mixed gas B that hydrogen producer gas transmission end exports；
S6, from hydrogen producer gas transmission end export part mixed gas A and B be delivered to separation chamber carry out separation output high-purity hydrogen
Gas.
The hydrogen production process for the instant hydrogen generating system of the methanol-water that the invention also provides further improvement, specifically include with
Lower step:
S1, the starting instant hydrogen generating system of methanol-water, raw material conveying device is by the first alcohol and water of the liquid in methanol-water storage container
It is delivered to the evaporator of hydrogen producer, the microwave heating equipment of evaporator carries out heating and gasifying to the first alcohol and water of liquid immediately,
Formation temperature reaches 100~350 DEG C of methanol vapor and vapor；
S2, temperature reach 100~350 DEG C of methanol vapor and vapor enter be placed with the reactor of low temperature catalyst for preparing hydrogen into
Row reaction hydrogen manufacturing, obtain containing hydrogen, carbon monoxide, carbon dioxide mixed gas A, and from hydrogen producer gas transmission end export；
The part mixed gas A exported from hydrogen producer gas transmission end is delivered to separation chamber and carries out separation output high-purity hydrogen A, high-purity
Hydrogen A is delivered to pressure buffer device and store for use；
S3, it is delivered to combustion furnace from the part mixed gas A that hydrogen producer gas transmission end exports, and/or defeated from pressure buffer device
The part high-purity hydrogen A of gas end output is delivered to combustion furnace, and combustion furnace passes through combust mixed gas A and/or high-purity hydrogen A
It is heated for evaporator, heater, so that the methanol vapor of evaporator gasification and vapor, by reactor but not yet completely
The methanol vapor and vapor of reaction are persistently overheating and finally maintenance temperature is 350~600 DEG C；
S4, the methanol vapor by heating and vapor carry out reaction system into the reactor for being placed with high temperature for hydrogen production catalyst
Hydrogen, obtain containing hydrogen, carbon monoxide, carbon dioxide mixed gas B, and from hydrogen producer gas transmission end export；It is set from hydrogen manufacturing
The part mixed gas B of standby gas transmission end output is delivered to separation chamber and carries out separating output high-purity hydrogen B, and high-purity hydrogen B is defeated
It send to pressure buffer device and store for use；
S5, it is delivered to combustion furnace from the part mixed gas B that hydrogen producer gas transmission end exports, and/or defeated from pressure buffer device
The part high-purity hydrogen B of gas end output is delivered to combustion furnace, circular flow step S3；
S6, pressure buffer device store for use to the high-purity hydrogen A and B that conveying comes, and will be high-purity through excess pressure control
Hydrogen is spent to export from its gas transmission end.
As the further improvement of the instant hydrogen generating system hydrogen production process of methanol-water of the present invention, when combustion furnace operation, evaporation
The microwave heating equipment of device is out of service or runs together with combustion furnace simultaneously.
After the instant hydrogen generating system starting of methanol-water of the present invention, by the existing methanol to liquid of the microwave heating equipment of evaporator
Heating and gasifying is carried out with water, forms methanol vapor and vapor, after system response produces hydrogen and runs combustion furnace, mainly by burning
Furnace provides thermal energy for evaporator, while can continue with microwave heating equipment auxiliary heating, convenient, flexible.
As the further improvement of the instant hydrogen generating system hydrogen production process of methanol-water of the present invention, the raw material conveying device to
The first alcohol and water of liquid provides the pressure of 2Mpa or more, preferably 5Mpa or more；The pressure buffer device gas transmission end output
The pressure of hydrogen is 2~6Mpa, preferably 2~3Mpa.
The pressure pressure of feedstock transportation link is improved, ensures that separation chamber's input terminal and output end have larger pressure difference, is promoted
Hydrogen gas output and rate.Pressure buffer device is able to achieve the control to output Hydrogen Vapor Pressure, the outlet of preferably 2~3Mpa pressure
Amount, is able to satisfy the needs of vehicle fuel battery.
As the further improvement of the instant hydrogen generating system hydrogen production process of methanol-water of the present invention, methanol vapor and water in step S3
Steam is persistently overheating and finally maintenance temperature is preferably 480~600 DEG C.
As the further improvement of the instant hydrogen generating system hydrogen production process of methanol-water of the present invention, the microwave of evaporator in step S3
Heating device carries out heating and gasifying to the first alcohol and water of liquid immediately, and formation temperature preferably reaches 120~200 DEG C of methanol vapor
And vapor.
Beneficial effects of the present invention:
1, the present invention is quick by internal microwave after cold start-up without solid hydrogen, gaseous hydrogen or the starting heating of other fuel
Heating and gasifying forms methanol vapor and vapor, recycles low temperature catalyst for preparing hydrogen to react hydrogen manufacturing in advance, to start hydrogen manufacturing system
It unites and rapidly enters good operation circulation, the case where reducing energy consumption, the starting speed greatly improved can be at 5 minutes
Inside reach complete starting.
2, the present invention is by methanol vapor and vapor multistage temperature control, guaranteeing in reaction process evaporator, heater
In be within the scope of stable optimal reaction temperature, guarantee hydrogen production reaction stable operation, hydrogen generating system operation it is more stable.
3, the present invention reduces the loss because of high temperature to catalyst, improves and be without heating to catalyst sustained combustion
The service life of system.
4, the present invention passes through the regulation of reaction temperature, pressure, especially with pressure buffer device to the pressure of output hydrogen
Control, solves the problems, such as that existing hydrogen generating system hydrogen output pressure is unstable or lower, while also solving existing hydrogen manufacturing system
System is difficult to the problem of controlling temperature.
5, present system and its hydrogen production process starting are fast, outlet is stable, loss is low, at low cost, provide significantly practical
Property, it can be applied to vehicle fuel battery.
Detailed description of the invention
Fig. 1 is the composition schematic diagram of the instant hydrogen generating system of 1 methanol-water of the embodiment of the present invention.
Fig. 2 is the composition schematic diagram of the instant hydrogen generating system of 2 methanol-water of the embodiment of the present invention.
Fig. 3 is the composition schematic diagram of the instant hydrogen generating system of 3 methanol-water of the embodiment of the present invention.
Specific embodiment
The following further describes the present invention with reference to the drawings.
Embodiment 1
The instant hydrogen generating system of methanol-water as shown in Figure 1, including methanol-water storage container, raw material conveying device, hydrogen producer, point
It is sequentially connected from room, and by pipeline；The first alcohol and water of liquid is stored in the methanol-water storage container (in liquid methanol water
Methanol accounts for the 62.5% of gross mass, and water accounts for the 37.5% of gross mass), and connect by raw material conveying device with hydrogen producer；It is described
Raw material conveying device can realize by the first alcohol and water in methanol-water storage container be delivered to hydrogen producer carry out hydrogen manufacturing；Described
The gas transmission end of separation chamber and hydrogen producer connection, be inside provided with membrane separation device, it can be achieved that hydrogen producer output gas into
Row separation output high-purity hydrogen.
The hydrogen producer of the instant hydrogen generating system of the methanol-water includes evaporator, 2 reactors and 2 heaters；Described
Evaporator is connect with raw material conveying device, reactor respectively, is built-in with microwave heating equipment；The instant hydrogen manufacturing system of the methanol-water
After system starting, liquid methanol and water progress heating and gasifying that microwave heating equipment can immediately come in raw material conveying device conveying.
The reactor and heater is cross-linked, and reactor is externally provided with the solid special energy-saving nanometer micropore material of thermal insulation material
Material；Low temperature catalyst for preparing hydrogen CuO/ZnO/CeO is placed in the reactor connecting with evaporator2/ZrO2, another reaction
High temperature for hydrogen production catalyst Pt/Al is placed in device2O3。
The instant hydrogen generating system of the methanol-water further includes the combustion furnace connecting with hydrogen producer gas transmission end；The methanol-water is
When hydrogen generating system starting after, combustion furnace is heated by gas made from burning hydrogen producer for evaporator, heater.
The method for preparing hydrogen using the instant hydrogen generating system of methanol-water described in the present embodiment 1, comprising the following steps:
S1, the starting instant hydrogen generating system of methanol-water, raw material conveying device is by the first alcohol and water of the liquid in methanol-water storage container
It is delivered to the evaporator of hydrogen producer, discharge pressure is 3~4Mpa, and the microwave heating equipment of evaporator is immediately to the methanol of liquid
Heating and gasifying is carried out with water, formation temperature reaches 200~300 DEG C of methanol vapor and vapor；
S2, temperature reach 200~300 DEG C of methanol vapor and vapor enter be placed with the reactor of low temperature catalyst for preparing hydrogen into
Row reaction hydrogen manufacturing, obtain containing hydrogen, carbon monoxide, carbon dioxide mixed gas A, and from hydrogen producer gas transmission end export；
S3, combustion furnace is delivered to from the mixed gas A that hydrogen producer gas transmission end exports, combustion furnace is to steam by combust mixed gas
Hair device, heater are heated so that the methanol vapor of evaporator gasification and vapor, by reactor but not yet reaction completely
Methanol vapor and vapor persistently overheating and finally maintain temperature be 400~600 DEG C；The microwave heating equipment of evaporator and combustion
Furnace is burnt to run together；
S4, the methanol vapor by heating and vapor carry out reaction system into the reactor for being placed with high temperature for hydrogen production catalyst
Hydrogen, obtain containing hydrogen, carbon monoxide, carbon dioxide mixed gas B, and from hydrogen producer gas transmission end export；
S5, combustion furnace, circular flow step S3 are delivered to from the part mixed gas B that hydrogen producer gas transmission end exports；
S6, from hydrogen producer gas transmission end export part mixed gas A and B be delivered to separation chamber carry out separation output high-purity hydrogen
Gas.
The operation logic of the present embodiment is:
Required according to the length of hydrogen producer pipeline and the control of final output Hydrogen Vapor Pressure etc., adjust the conveying of raw material conveying device
Pressure is 3~4Mpa, the first alcohol and water of liquid is delivered in the evaporator of hydrogen producer, the microwave heating equipment of evaporator is
When heating and gasifying form methanol vapor and vapor.Due to being to heat immediately, the temperature of methanol vapor and vapor cannot be instantaneous
Promotion is too high, can be in more low-temperature condition.According to the optimal reaction temperature of low temperature catalyst, selection or adjusting microwave heating
The heating power of device makes methanol vapor and vapor reach 200~300 DEG C of best low-temp reaction temperature.200~300 DEG C of first
Alcohol vapor and vapor are by being placed with low temperature catalyst for preparing hydrogen CuO/ZnO/CeO2/ZrO2Reactor after start react hydrogen manufacturing,
Obtain containing hydrogen, carbon monoxide, carbon dioxide mixed gas A.Since membrane separation device has not yet been reached in mixed gas A temperature
Reaction temperature, mixed gas A all send to combustion furnace, and combustion furnace passes through combust mixed gas continuous service microwave heating simultaneously
Device is that evaporator, heater are heated, so that the methanol vapor of evaporator gasification and vapor, by reactor but not yet
The methanol vapor and vapor reacted completely are persistently overheating and finally maintenance temperature is 400~600 DEG C, i.e. optimal reactive temperature.
400~600 DEG C of methanol vapor and vapor, which enters, is placed with high temperature for hydrogen production catalyst Pt/Al2O3Reactor after start to react
Hydrogen manufacturing, obtain containing hydrogen, carbon monoxide, carbon dioxide mixed gas B, realize system benign cycle.Gaseous mixture at this time
Body a part continues for running combustion furnace, and a part enters the isolated high-purity hydrogen in separation chamber, and hydrogen output pressure is 2
~3MPa can provide sufficient hydrogen for vehicle fuel battery.
Embodiment 2
The instant hydrogen generating system of methanol-water as shown in Figure 2, including methanol-water storage container, raw material conveying device, hydrogen producer, point
It is sequentially connected from room and pressure buffer device, and by pipeline；In the methanol-water storage container store liquid methanol and
Water (methanol accounts for the 62.5% of gross mass in liquid methanol water, and water accounts for the 37.5% of gross mass), and pass through raw material conveying device and system
Hydrogen storage equipment connection；The raw material conveying device, which can be realized, is delivered to hydrogen producer for the first alcohol and water in methanol-water storage container
Carry out hydrogen manufacturing；The gas transmission end of the separation chamber and hydrogen producer connects, and is inside provided with membrane separation device, it can be achieved that setting to hydrogen manufacturing
The gas of standby output carries out separation output high-purity hydrogen.
The hydrogen producer of the instant hydrogen generating system of the methanol-water includes evaporator, 4 reactors and 4 heaters；Described
Evaporator is connect with raw material conveying device, reactor respectively, is built-in with microwave heating equipment；The instant hydrogen manufacturing system of the methanol-water
After system starting, liquid methanol and water progress heating and gasifying that microwave heating equipment can immediately come in raw material conveying device conveying；
The reactor and heater is cross-linked, and reactor is externally provided with mineral wool thermal insulation material；It is described to be connect with evaporator
Low temperature catalyst for preparing hydrogen CuO/ZnO/Al is placed in preceding 2 reactors2O3/ZrO2, high temperature for hydrogen production is placed in remaining reactor
Catalyst Pd/ZnO/Al2O3。
The pressure buffer device is connect with separation chamber's gas transmission end, and pressure buffer device is able to achieve to output hydrogen pressure
The control of power；
It further include the combustion furnace being connect with pressure buffer device gas transmission end；After the instant hydrogen generating system starting of the methanol-water, combustion
The gas that furnace is exported by combustion pressure buffer unit is burnt to be heated for evaporator, heater.
The method for preparing hydrogen using the instant hydrogen generating system of methanol-water described in the present embodiment 2, comprising the following steps:
S1, the starting instant hydrogen generating system of methanol-water, raw material conveying device is by the first alcohol and water of the liquid in methanol-water storage container
It is delivered to the evaporator of hydrogen producer, discharge pressure is 2~3MPa, and the microwave heating equipment of evaporator is immediately to the methanol of liquid
Heating and gasifying is carried out with water, formation temperature reaches 350 DEG C of methanol vapor and vapor；
S2, temperature reach 350 DEG C of methanol vapor and vapor carries out instead into the reactor for being placed with low temperature catalyst for preparing hydrogen
Answer hydrogen manufacturing, obtain containing hydrogen, carbon monoxide, carbon dioxide mixed gas A, and from hydrogen producer gas transmission end export；From system
The part mixed gas A of hydrogen storage equipment gas transmission end output is delivered to separation chamber and carries out separation output high-purity hydrogen A, high-purity hydrogen
A is delivered to pressure buffer device and store for use；
S3, combustion furnace is delivered to from the part high-purity hydrogen A that pressure buffer device gas transmission end exports, combustion furnace is high by burning
Purity hydrogen A is that evaporator, heater are heated so that the methanol vapor of evaporator gasification and vapor, by reactor
But the methanol vapor and vapor not yet reacted completely are persistently overheating and finally maintenance temperature is 400~600 DEG C；Evaporator it is micro-
Wave heating device is out of service；
S4, the methanol vapor by heating and vapor carry out reaction system into the reactor for being placed with high temperature for hydrogen production catalyst
Hydrogen, obtain containing hydrogen, carbon monoxide, carbon dioxide mixed gas B, and from hydrogen producer gas transmission end export；It is set from hydrogen manufacturing
The part mixed gas B of standby gas transmission end output is delivered to separation chamber and carries out separating output high-purity hydrogen B, and high-purity hydrogen B is defeated
It send to pressure buffer device and store for use；
S5, combustion furnace, circular flow step S3 are delivered to from the part high-purity hydrogen B that pressure buffer device gas transmission end exports；
S6, pressure buffer device store for use to the high-purity hydrogen A and B that conveying comes, and will be high-purity through excess pressure control
Hydrogen is spent to export from its gas transmission end.
The operation logic of the present embodiment is:
Required according to the length of hydrogen producer pipeline and the control of final output Hydrogen Vapor Pressure etc., adjust the conveying of raw material conveying device
Pressure is 2~3Mpa, the first alcohol and water of liquid is delivered in the evaporator of hydrogen producer, the microwave heating equipment of evaporator is
When heating and gasifying form methanol vapor and vapor.Due to being to heat immediately, the temperature of methanol vapor and vapor cannot be instantaneous
Promotion is too high, can be in more low-temperature condition.According to the optimal reaction temperature of low temperature catalyst, selection or adjusting microwave heating
The heating power of device makes methanol vapor and vapor reach 350 DEG C of best low-temp reaction temperature.350 DEG C of methanol vapor and water
Steam is by being placed with low temperature catalyst for preparing hydrogen CuO/ZnO/Al2O3/ZrO2Reactor after start react hydrogen manufacturing, contained
Hydrogen, carbon monoxide, carbon dioxide mixed gas A, mixed gas A enters the hydrogen that separation chamber carries out isolated high-purity
A, high-purity hydrogen A are delivered to pressure buffer device and store for use.A part of high-purity hydrogen A is sent from pressure buffer device
To combustion furnace, combustion furnace is heated by burning high-purity hydrogen A for evaporator, heater, so that the first of evaporator gasification
Alcohol vapor and vapor, the methanol vapor by reactor but not yet reacted completely and vapor persistently overheating simultaneously finally maintain temperature
Degree is 400~600 DEG C, i.e. optimal reactive temperature.400~600 DEG C of methanol vapor and vapor, which enters, is placed with high temperature for hydrogen production
Catalyst Pd/ZnO/Al2O3Reactor after start react hydrogen manufacturing, obtain the mixing containing hydrogen, carbon monoxide, carbon dioxide
Gas B realizes system benign cycle.Mixed gas a part at this time continues for running combustion furnace, and a part enters separation
The isolated high-purity hydrogen in room, hydrogen output pressure are 2~3MPa, and sufficient hydrogen can be provided for vehicle fuel battery.
Embodiment 3
The instant hydrogen generating system of methanol-water as shown in Figure 3, including methanol-water storage container, raw material conveying device, hydrogen producer, point
It is sequentially connected from room and pressure buffer device, and by pipeline；In the methanol-water storage container store liquid methanol and
Water (methanol accounts for the 62.5% of gross mass in liquid methanol water, and water accounts for the 37.5% of gross mass), and pass through raw material conveying device and system
Hydrogen storage equipment connection；The raw material conveying device, which can be realized, is delivered to hydrogen producer for the first alcohol and water in methanol-water storage container
Carry out hydrogen manufacturing；The gas transmission end of the separation chamber and hydrogen producer connects, and is inside provided with membrane separation device, it can be achieved that setting to hydrogen manufacturing
The gas of standby output carries out separation output high-purity hydrogen.
The hydrogen producer of the instant hydrogen generating system of the methanol-water includes evaporator, 6 reactors and 6 heaters；Described
Evaporator is connect with raw material conveying device, reactor respectively, is built-in with microwave heating equipment；The instant hydrogen manufacturing system of the methanol-water
After system starting, liquid methanol and water progress heating and gasifying that microwave heating equipment can immediately come in raw material conveying device conveying；
The reactor and heater is cross-linked, and reactor is externally provided with porcelain tendre thermal insulation material；It is described to connect with evaporator
Low temperature catalyst for preparing hydrogen CuO/ZnO/CeO is placed in preceding 2 reactors and last 1 reactor2/ZrO2, in remaining reactor
It is placed with high temperature for hydrogen production catalyst Z n-Cr/Al2O3。
The pressure buffer device is connect with separation chamber's gas transmission end, and pressure buffer device is able to achieve to output hydrogen pressure
The control of power；
It further include the combustion furnace being connect with hydrogen producer and pressure buffer device gas transmission end；The instant hydrogen generating system of the methanol-water
After starting, combustion furnace is by burning hydrogen producer and the gas of pressure buffer device output is evaporator, heater is heated.
The method for preparing hydrogen using the instant hydrogen generating system of methanol-water described in the present embodiment 3, comprising the following steps:
S1, the starting instant hydrogen generating system of methanol-water, raw material conveying device is by the first alcohol and water of the liquid in methanol-water storage container
It is delivered to the evaporator of hydrogen producer, discharge pressure is 5~6MPa, and the microwave heating equipment of evaporator is immediately to the methanol of liquid
Heating and gasifying is carried out with water, formation temperature reaches 100~200 DEG C of methanol vapor and vapor；
S2, temperature reach 100~200 DEG C of methanol vapor and vapor enter be placed with the reactor of low temperature catalyst for preparing hydrogen into
Row reaction hydrogen manufacturing, obtain containing hydrogen, carbon monoxide, carbon dioxide mixed gas A, and from hydrogen producer gas transmission end export；
The mixed gas A exported from hydrogen producer gas transmission end is delivered to combustion furnace, combustion furnace by combust mixed gas A be evaporator,
Heater is heated, so that mixed gas A is warming up to 350 DEG C or more and exports from hydrogen producer gas transmission end；From hydrogen producer
The part mixed gas A of gas transmission end output is delivered to separation chamber and carries out separation output high-purity hydrogen A, high-purity hydrogen A conveying
Store to pressure buffer device stand-by；
S3, combustion furnace is delivered to from the part mixed gas A that hydrogen producer gas transmission end exports, and from pressure buffer device gas transmission end
The part high-purity hydrogen A of output is delivered to combustion furnace, and combustion furnace is evaporation by combust mixed gas A and high-purity hydrogen A
Device, heater are heated, so that the methanol vapor of evaporator gasification and vapor, by reactor but not yet reacting completely
Methanol vapor and vapor persistently overheating and finally maintain temperature be 480~600 DEG C；The microwave heating equipment of evaporator is after reforwarding
Row；
S4, the methanol vapor by heating and vapor carry out reaction system into the reactor for being placed with high temperature for hydrogen production catalyst
Hydrogen, obtain containing hydrogen, carbon monoxide, carbon dioxide mixed gas B, and from hydrogen producer gas transmission end export；It is set from hydrogen manufacturing
The part mixed gas B of standby gas transmission end output is delivered to separation chamber and carries out separating output high-purity hydrogen B, and high-purity hydrogen B is defeated
It send to pressure buffer device and store for use；
S5, combustion furnace is delivered to from the part mixed gas B that hydrogen producer gas transmission end exports, and from pressure buffer device gas transmission end
The part high-purity hydrogen B of output is delivered to combustion furnace, circular flow step S3；
S6, pressure buffer device store for use to the high-purity hydrogen A and B that conveying comes, and will be high-purity through excess pressure control
Hydrogen is spent to export from its gas transmission end.
The operation logic of the present embodiment is:
Required according to the length of hydrogen producer pipeline and the control of final output Hydrogen Vapor Pressure etc., adjust the conveying of raw material conveying device
Pressure is 5~6Mpa, the first alcohol and water of liquid is delivered in the evaporator of hydrogen producer, the microwave heating equipment of evaporator is
When heating and gasifying form methanol vapor and vapor.Due to being to heat immediately, the temperature of methanol vapor and vapor cannot be instantaneous
Promotion is too high, can be in more low-temperature condition.According to the optimal reaction temperature of low temperature catalyst, selection or adjusting microwave heating
The heating power of device makes methanol vapor and vapor reach 100~200 DEG C of best low-temp reaction temperature.100~200 DEG C of first
Alcohol vapor and vapor are by being placed with low temperature catalyst for preparing hydrogen CuO/ZnO/CeO2/ZrO2Reactor after start react hydrogen manufacturing,
Obtain containing hydrogen, carbon monoxide, carbon dioxide mixed gas A.Since membrane separation device has not yet been reached in mixed gas A temperature
Reaction temperature, mixed gas A all send to combustion furnace, and combustion furnace passes through combust mixed gas continuous service microwave heating simultaneously
Device is that evaporator, heater are heated, so that mixed gas A is warming up to 350 DEG C or more and defeated from hydrogen producer gas transmission end
Out.350 DEG C of mixed gas A enter the hydrogen A that separation chamber carries out isolated high-purity, and it is slow that high-purity hydrogen A is delivered to pressure
Flushing device store stand-by.By the part mixed gas A exported from hydrogen producer gas transmission end and from pressure buffer device gas transmission
The part high-purity hydrogen A of end output is delivered to combustion furnace, and combustion furnace is to steam by combust mixed gas A and high-purity hydrogen A
Hair device, heater are heated so that the methanol vapor of evaporator gasification and vapor, by reactor but not yet reaction completely
Methanol vapor and vapor persistently overheating and finally to maintain temperature be 480~600 DEG C, i.e. optimal reactive temperature.480~600
DEG C DEG C methanol vapor and vapor enter be placed with high temperature for hydrogen production catalyst Z n-Cr/Al2O3Reactor after start reaction system
Hydrogen, obtain containing hydrogen, carbon monoxide, carbon dioxide mixed gas B, realize system benign cycle.Mixed gas at this time
A part continues for running combustion furnace, and a part enters the isolated high-purity hydrogen in separation chamber, and hydrogen output pressure is 2~
3MPa can provide sufficient hydrogen for vehicle fuel battery.
Description in embodiment and application be it is illustrative, be not wishing to limit the scope of the invention to above-described embodiment
In.The deformation and change of embodiments disclosed herein are possible, the realities for those skilled in the art
The replacement and equivalent various parts for applying example are well known.It should be appreciated by the person skilled in the art that not departing from the present invention
Spirit or essential characteristics in the case where, the present invention can in other forms, structure, arrangement, ratio, and with other components,
Material and component are realized.Without departing from the scope and spirit of the present invention, can to embodiments disclosed herein into
The other deformations of row and change.
Claims (10)
1. a kind of instant hydrogen generating system of methanol-water, including methanol-water storage container, raw material conveying device, hydrogen producer, separation chamber；
The first alcohol and water of liquid is stored in the methanol-water storage container, and is connect by raw material conveying device with hydrogen producer；Institute
The raw material conveying device stated can realize that the first alcohol and water in methanol-water storage container, which is delivered to hydrogen producer, carries out hydrogen manufacturing；It is described
Separation chamber and hydrogen producer gas transmission end connect, be inside provided with membrane separation device, it can be achieved that hydrogen producer output gas
Carry out separation output high-purity hydrogen；It is characterized by:
The hydrogen producer includes evaporator, several reactors and several heaters；The reactor and heater
It is cross-linked, catalyst for preparing hydrogen is placed in reactor；
The evaporator is connect with raw material conveying device, reactor respectively, is built-in with microwave heating equipment；The methanol-water
After instant hydrogen generating system starting, microwave heating equipment can convey the liquid methanol come in raw material conveying device immediately and water carries out
Heating and gasifying；
It further include the combustion furnace being connect with hydrogen producer gas transmission end；After the instant hydrogen generating system starting of the methanol-water, combustion furnace
The gas as made from burning hydrogen producer is evaporator, heater is heated.
2. a kind of instant hydrogen generating system of methanol-water, including methanol-water storage container, raw material conveying device, hydrogen producer, separation chamber；
The first alcohol and water of liquid is stored in the methanol-water storage container, and is connect by raw material conveying device with hydrogen producer；Institute
The raw material conveying device stated can realize that the first alcohol and water in methanol-water storage container, which is delivered to hydrogen producer, carries out hydrogen manufacturing；It is described
Separation chamber and hydrogen producer gas transmission end connect, be inside provided with membrane separation device, it can be achieved that hydrogen producer output gas
Carry out separation output high-purity hydrogen；It is characterized by:
The hydrogen producer includes evaporator, several reactors and several heaters；The reactor and heater
It is cross-linked, catalyst for preparing hydrogen is placed in reactor；
The evaporator is connect with raw material conveying device, reactor respectively, is built-in with microwave heating equipment；The methanol-water
After instant hydrogen generating system starting, microwave heating equipment can convey the liquid methanol come in raw material conveying device immediately and water carries out
Heating and gasifying；
It further include the pressure buffer device being connect with separation chamber's gas transmission end, the pressure buffer device is able to achieve to output hydrogen
The control of pressure；
It further include the combustion furnace being connect with hydrogen producer and/or pressure buffer device gas transmission end；The instant hydrogen manufacturing of the methanol-water
System starting after, combustion furnace by burning hydrogen producer and/or pressure buffer device output gas be evaporator, heater into
Row heating.
3. any instant hydrogen generating system of methanol-water according to claim 1~2, it is characterised in that: the reactor number
Amount at least two, the heater quantity at least two.
4. the instant hydrogen generating system of methanol-water according to claim 3, it is characterised in that: placed at least one reactor
There is low temperature catalyst for preparing hydrogen, high temperature for hydrogen production catalyst is placed in remaining reactor.
5. the instant hydrogen generating system of methanol-water according to claim 4, it is characterised in that: the reactor is externally provided with heat preservation
Heat-barrier material.
6. the hydrogen production process of the instant hydrogen generating system of methanol-water as claimed in claim 5, it is characterised in that: the following steps are included:
S1, the starting instant hydrogen generating system of methanol-water, raw material conveying device is by the first alcohol and water of the liquid in methanol-water storage container
It is delivered to the evaporator of hydrogen producer, the microwave heating equipment of evaporator carries out heating and gasifying to the first alcohol and water of liquid immediately,
Formation temperature reaches 100~350 DEG C of methanol vapor and vapor；
S2, temperature reach 100~350 DEG C of methanol vapor and vapor enter be placed with the reactor of low temperature catalyst for preparing hydrogen into
Row reaction hydrogen manufacturing, obtain containing hydrogen, carbon monoxide, carbon dioxide mixed gas A, and from hydrogen producer gas transmission end export；
S3, it is delivered to combustion furnace from the part mixed gas A that hydrogen producer gas transmission end exports, combustion furnace passes through combust mixed gas
It is heated for evaporator, heater, so that the methanol vapor of evaporator gasification and vapor, by reactor but not yet completely
The methanol vapor and vapor of reaction are persistently overheating and finally maintenance temperature is 350~600 DEG C；
S4, the methanol vapor by heating and vapor carry out reaction system into the reactor for being placed with high temperature for hydrogen production catalyst
Hydrogen, obtain containing hydrogen, carbon monoxide, carbon dioxide mixed gas B, and from hydrogen producer gas transmission end export；
S5, combustion furnace, circular flow step S3 are delivered to from the part mixed gas B that hydrogen producer gas transmission end exports；
S6, from hydrogen producer gas transmission end export part mixed gas A and B be delivered to separation chamber carry out separation output high-purity hydrogen
Gas.
7. the hydrogen production process of the instant hydrogen generating system of methanol-water as claimed in claim 5, it is characterised in that: the following steps are included:
S1, the starting instant hydrogen generating system of methanol-water, raw material conveying device is by the first alcohol and water of the liquid in methanol-water storage container
It is delivered to the evaporator of hydrogen producer, the microwave heating equipment of evaporator carries out heating and gasifying to the first alcohol and water of liquid immediately,
Formation temperature reaches 100~350 DEG C of methanol vapor and vapor；
S2, temperature reach 100~350 DEG C of methanol vapor and vapor enter be placed with the reactor of low temperature catalyst for preparing hydrogen into
Row reaction hydrogen manufacturing, obtain containing hydrogen, carbon monoxide, carbon dioxide mixed gas A, and from hydrogen producer gas transmission end export；
The part mixed gas A exported from hydrogen producer gas transmission end is delivered to separation chamber and carries out separation output high-purity hydrogen A, high-purity
Hydrogen A is delivered to pressure buffer device and store for use；
S3, it is delivered to combustion furnace from the part mixed gas A that hydrogen producer gas transmission end exports, and/or defeated from pressure buffer device
The part high-purity hydrogen A of gas end output is delivered to combustion furnace, and combustion furnace passes through combust mixed gas A and/or high-purity hydrogen A
It is heated for evaporator, heater, so that the methanol vapor of evaporator gasification and vapor, by reactor but not yet completely
The methanol vapor and vapor of reaction are persistently overheating and finally maintenance temperature is 350~600 DEG C；
S4, the methanol vapor by heating and vapor carry out reaction system into the reactor for being placed with high temperature for hydrogen production catalyst
Hydrogen, obtain containing hydrogen, carbon monoxide, carbon dioxide mixed gas B, and from hydrogen producer gas transmission end export；It is set from hydrogen manufacturing
The part mixed gas B of standby gas transmission end output is delivered to separation chamber and carries out separating output high-purity hydrogen B, and high-purity hydrogen B is defeated
It send to pressure buffer device and store for use；
S5, it is delivered to combustion furnace from the part mixed gas B that hydrogen producer gas transmission end exports, and/or defeated from pressure buffer device
The part high-purity hydrogen B of gas end output is delivered to combustion furnace, circular flow step S3；
S6, pressure buffer device store for use to the high-purity hydrogen A and B that conveying comes, and will be high-purity through excess pressure control
Hydrogen is spent to export from its gas transmission end.
8. the hydrogen production process of any instant hydrogen generating system of methanol-water of according to claim 6 or 7, it is characterised in that: work as combustion
When burning furnace operation, the microwave heating equipment of evaporator is out of service or runs together with combustion furnace simultaneously.
9. the hydrogen production process of the instant hydrogen generating system of methanol-water according to claim 8, it is characterised in that: the raw material is defeated
Device is sent to provide the pressure of 2Mpa or more to the first alcohol and water of liquid, the hydrogen of the pressure buffer device gas transmission end output
Pressure is 2~6MPa.
10. the hydrogen production process of the instant hydrogen generating system of methanol-water according to claim 8, it is characterised in that: the step S3
Middle methanol vapor and vapor persistently overheating and finally maintain temperature be 480~600 DEG C.
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| CN111056532A (en) * | 2020-02-26 | 2020-04-24 | 上海舵杰汽车检测仪器有限公司 | Methanol decomposition hydrogen production device |
| CN111377403A (en) * | 2020-04-23 | 2020-07-07 | 广东大昆科技有限公司 | Quiet compact movable methanol low-temperature liquid-phase reforming hydrogen production system |
| CN112960645A (en) * | 2019-12-14 | 2021-06-15 | 中国科学院大连化学物理研究所 | Water-steam shift reactor for autothermal reforming hydrogen production reaction and method for improving CO conversion rate of water-steam shift reaction |
| CN113233418A (en) * | 2021-05-14 | 2021-08-10 | 广州氢动科技有限公司 | Method and equipment for preparing hydrogen from efficient methanol solution |
| CN114162782A (en) * | 2021-11-24 | 2022-03-11 | 德州新动能铁塔发电有限公司 | Hydrogen production equipment and method |
| CN116654870A (en) * | 2023-06-16 | 2023-08-29 | 北京理工大学 | Self-heating type method for preparing hydrogen by reforming green alcohol and alcohol water solution |
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