CN104591086B - With the method and system of gas hydrates hydrogen manufacturing in situ in hydrogen cell automobile - Google Patents
With the method and system of gas hydrates hydrogen manufacturing in situ in hydrogen cell automobile Download PDFInfo
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Abstract
The present invention relates to the method and system with gas hydrates hydrogen manufacturing in situ in a kind of hydrogen cell automobile.The method comprises the following steps: the water vapour obtained by gas hydrate dissociation and natural gas preheating, then product gas is prepared with steam reforming catalysts haptoreaction, product gas after cooling and carbon monoxide transformation catalyst haptoreaction, prepare conversion gas, conversion gas is carried out membrance separation purification, obtain high-purity hydrogen, after hydrogen_cooling, input hydrogen fuel cell；It addition, present invention also offers the small size system of a kind of gas hydrates hydrogen manufacturing in situ, including: gas hydrates feedway, steam reformer, carbon monoxide conversion device, membrance separation purified hydrogen device, chiller and hydrogen fuel cell.Utilize the technical scheme that the present invention provides, be not required to build substantial amounts of hydrogenation stations and on automobile, fill high pressure hydrogen holding vessel, i.e. may be implemented in hydrogen manufacturing in situ in hydrogen cell automobile, reduced investment, expand resistance little.
Description
Technical field
The invention belongs to new-energy automobile field, be specifically related in a kind of hydrogen cell automobile former with gas hydrates
The method and system of position hydrogen manufacturing.
Background technology
2010, China replaces the U.S. became the automobile market that the whole world is maximum.The emergence of China Auto Market will be in future
The opportunity that a very long time is brought is surprising.Gaosheng was once issued a about following Global Auto turn of the market
Report.2000, the U.S. had 1.35 hundred million automobiles, and China only has 8,500,000,5,400,000, India.High
Containing and estimate, to the year two thousand fifty, will there be 2.33 hundred million automobiles, 5.14 hundred million, China, 6.1 hundred million, India in the U.S..It is difficult to
The imagination, the demand of oil will be had much by the most vehicles in the whole world.The demand of fuel is constantly increased by Asia, meaning
And have to find other fuel future, or develop other alternative energies.
But Beijing and other metropolitan reality of the world are it has been shown that the existing auto industry of immoderate development, car tail
The haze that conductance causes will bring huge challenge, solution to be to substitute transition of auto industry, i.e. to electric automobile and
Hydrogen cell automobile develops.
The most current fuel-engined vehicle upgrades to electric automobile and hydrogen cell automobile, at following 5-20 suddenly
Have one day we must in the face of this reality, how industrial gas oil provides for a rainy day？American energy information administration is up-to-date
Data show, the peak value that the gasoline consumption of the U.S. in 2013 reached compared to 1998, have dropped nearly
75%, and everything only occurs in the time of about 15 years, whether this phenomenon can occur in China？
The energy development history of the mankind is from fuel wood → coal → natural gas → biogas → hydrogen, although this path is the most disputable,
But energy form that free from controversy is from be affixed to liquid again to gas, natural gas, biogas and hydrogen and electricity will be future automobile
Main energy sources supply form.
For hydrogen manufacturing, raw material is renewable, can be by water electrolysis hydrogen producing, i.e. by water hydrogen manufacturing, but modern age from gasoline, diesel oil and
The combustion powered car such as gas-fueled vehicles, in Hydrogen Fuel-cell Vehicles transition, must have the transition stage of one section of alkane hydrogen manufacturing.
In the route of alkane hydrogen manufacturing, especially best with natural gas steam reforming hydrogen manufacturing effect, the not only H/C in methane
The highest, and this technique also converts the hydrogen in water to come, and make use of the hydrogen hydrogen producing in next life in water.
Gas hydrates (NGH), are also called combustible ice, are natural gas and water (temperature, pressure under certain condition
Power, gas saturation, salinity etc.) white crystalline compound that formed.The NGH of one unit volume can storage standard
The natural gas of the lower 180 times of volumes of state, memory space is little.NGH is as a kind of novel potential energy source, and reserves are huge
Greatly, be equivalent to about 2.84 times of non-renewable energy (coal, oil, natural gas etc.) reserves, the whole world it is considered to be
Have most application prospect can one of new forms of energy of fossil energy such as petroleum replacing, and extensively found to be present in sea
Bottom sediment and land permafrost region.Gas hydrates can be at normal pressure, store in the range of-20 DEG C to 30 DEG C, and one
Decompose under fixed heating or pressure-lowering condition.
But the bottleneck of development hydrogen cell automobile is the supply of hydrogen, need newly-built substantial amounts of automobile hydrogenation stations and
Hydrogen manufacturing, dispensing and storage facilities, the most also need to install high pressure hydrogen storage tank onboard.And, with existing gasoline and
The supply technique of natural gas, equipment are compared, and owing to hydrogen is the lightest element, it produces, transports and storage cost height,
Also it is one of factor restricting hydrogen energy fuel battery industry.
Summary of the invention
For solving the problems referred to above, it is an object of the invention to provide and use gas hydrates in a kind of hydrogen cell automobile
The method of hydrogen manufacturing in situ, by the gas hydrate dissociation stored on automobile is obtained natural gas and water vapour, is urging
Reacting under the effect of agent, the hydrogen in methane and water is converted hydrogen, hydrogen directly feeds the hydrogen fuel cell of automobile and sends out
Electricity.
Another object of the present invention is to provide one with gas hydrates hydrogen manufacturing in situ in hydrogen cell automobile
System.
For reaching above-mentioned purpose, the invention provides in a kind of hydrogen cell automobile with gas hydrates hydrogen manufacturing in situ
Method, it comprises the following steps: the water vapour obtained by gas hydrate dissociation and natural gas output, gas warp
Mixing after preheating, then prepare product gas with steam reforming catalysts haptoreaction, wherein, reaction pressure is
0.1-2.0MPa, temperature is 450-1200 DEG C, CH4Air speed is 500-5000h-1, steam/hydrocarbons ratio (H2O/C mol ratio)
For 2-6；
Make, through overcooled product gas and carbon monoxide transformation catalyst haptoreaction, to prepare conversion gas, wherein, reaction
Pressure is 0.1-2.0MPa, and temperature is 300-500 DEG C, and air speed is 500-2000h-1；
Conversion gas is carried out membrance separation purification, obtain CO content≤50ppm hydrogen and separate after tail gas, cooling
After, hydrogen is inputted hydrogen fuel cell.
Water vapour that the gas hydrate dissociation stored on automobile is obtained by this method and natural gas are at the work of catalyst
With lower prepared hydrogen, supply the hydrogen fuel cell generating of automobile after hydrogen purification, it is achieved that in hydrogen cell automobile
Hydrogen manufacturing in situ.This method is to use steam reforming catalysts that the methane in natural gas and the hydrogen in water are converted hydrogen, makes
Reduce carbon monoxide gas body burden in product gas with carbon monoxide transformation catalyst, then obtain height by membrane separation process
Purity hydrogen.
In the above-mentioned methods, it is preferable that described steam reforming catalysts is M/Al2O3, wherein, M is active component,
It is the combination of one or more in Pt, Pd, Rh, Ag and Ru, Al2O3For carrier, with Al2O3Quality
Meter, the content of M is 0.5-2.0wt%.Preferably, active component M directly can be carried on Al2O3Material anti-
Should be on pipe, now Al2O3It is carrier, is again the reaction tube of reactor.
In the above-mentioned methods, it is preferable that by weight percentage, described carbon monoxide transformation catalyst has following group
Part: 5-10wt%Cr2O3, 5-10wt%Co3O4, remaining be ferrum oxide.
In the above-mentioned methods, it is preferable that the total sulfur content≤0.1ppm of described gas hydrates；Described membrance separation carries
Pure temperature is 300-500 DEG C, at this temperature, can use noble metal film that conversion gas carries out middle temperature and separate, separate
Efficiency is high.
In the above-mentioned methods, it is preferable that (such as, film divides can to use the condensed water in additional deionized water or system
Hydrogen after purifying and the cooled water separated of tail gas) to steam reforming reaction, (water vapour and natural gas turn with steam
Change catalyst haptoreaction) carry out moisturizing, these water can also be used for the humidification of hydrogen fuel cell.
In the above-mentioned methods, the mixing unstripped gas of preheating enters steam reformer by the road and carries out pyrolytic conversion, and it produces
Product gas through heat exchange cool down after through connection pipeline enter CO converting means react further to reduce CO content；
Medium temperature and medium pressure conversion gas enter by the road membrane separator carry out hydrogen purification with prepare meet proton membrane fuel battery work
The high-purity hydrogen of condition, and be down to low temperature enter by the road hydrogen gas buffer enter back into membrane cell anode participate in send out
Electricity reaction, and another part tail gas can enter steam reformer by the road after heat exchange cools down and carry out combustion heating；
Through the air entrance fuel battery negative pole participation electric power generation reaction of filtration, purification, the water that reaction generates is expelled directly out outside car or quilt
Other motor vehicle assemblies recycle.
In the above-mentioned methods, it is achieved the key of vehicle-mounted original position hydrogen manufacturing essentially consists in two aspects: 1, steam reforming reaction is adopted
Reaction efficiency is substantially increased with noble metal catalyst, and only with one-level Carbon Monoxide Shift Reaction so that steam
Convert and carbon monodixe conversion device can miniaturization, be suitable to vehicle-mounted；2, it is different from general organic membrane and separates institute
The room temperature condition required, in this method, conversion gas is to enter noble metal film at relatively high temperatures to carry out the separation of middle temperature, it is possible to
Isolate hydrogen efficiently, meet the needs of on-board hydrogen generation system.
Present invention also offers a kind of system with gas hydrates hydrogen manufacturing in situ in hydrogen cell automobile, it is special
Levying and be, this system includes:
Gas hydrates feedway, steam reformer, carbon monoxide conversion device, membrance separation purified hydrogen device,
Chiller and hydrogen fuel cell；
Described gas hydrates feedway connects with described steam reformer, and described steam reformer is with described
Carbon monoxide conversion device connects, and described carbon monoxide conversion device connects with described membrance separation purified hydrogen device, described
Membrance separation purified hydrogen device connects with described chiller, and described chiller connects with described hydrogen fuel cell, respectively fills
Put with corresponding control system or controller, to realize the control of the correlation function for each device；
Described gas hydrates feedway be provided with gas hydrates bin, heating assembly, gas pipeline,
Decomposition water bin and water vapour pipeline；
Described steam reformer includes preheating assembly, cooling assembly, burning heater and reactor, described reactor
For calandria type fixed bed reactor, on the reaction tube of this calandria type fixed bed reactor, deposition has steam reforming catalysts
Active component, the entrance of described preheating assembly respectively with gas pipeline and the water vapour of gas hydrates feedway
Pipeline connection, the outlet of preheating assembly connects with the entrance of reactor；The entrance of described cooling assembly goes out with reactor
Mouth connection, the described outlet of cooling assembly connects with the entrance of carbon monoxide conversion device, the combustion of described burning heater
Material pipeline connects with feeder and/or chiller.
The preheating assembly of described steam reformer and cooling assembly can consist of product Gas Cooler, and it is handed over by heat
Change heated natural gas and water vapour, simultaneously cooling product gas；Described burning heater provides heat for conversion reaction, its
Fuel can be the tail gas after natural gas and/or the cooling of cooled device；The temperature of steam reforming reaction control to be divided into into
Mouthful temperature controls and outlet temperature controls, inlet temperature by the preheating temperature of unstripped gas is controlled, outlet temperature
It is controlled by the heat of supply steam conversion zone.
Described gas hydrates feedway is for the offer natural gas quantitative to steam reformer and water vapour, tool
Body is: gas hydrates bin be used for storing natural gas hydrate, its by heating assembly discharge natural gas and
Water, water enters in decomposition water bin, and is vaporizated into water vapour, natural gas and water vapour by stream by heating assembly
Amount control system is by quantitative output.
Described steam reformer is used for making natural gas and water vapour and steam reforming catalysts haptoreaction, thus at this
Preparing product gas under the catalytic action of catalyst, natural gas and water vapour can mix after preheating respectively again.
Described carbon monoxide conversion device is used for making product gas and carbon monoxide transformation catalyst haptoreaction, makes product gas
The content of middle carbon monoxide reduces, and the gas that reaction obtains is referred to as conversion gas.
Described membrance separation purified hydrogen device for the Hydrogen Separation in conversion gas being gone out, is wanted being met hydrogen fuel cell
The high-purity hydrogen asked, obtains the tail gas after separating hydrogen simultaneously.
In said system, it is preferable that described chiller includes heat exchanger, its by heat exchange cooled hydrogen and
Tail gas, and for gas hydrates device heating assembly provide heat.Other heat-producing unit intrasystem is alternatively sky
So the heating assembly of gas hydrate feedway provides the cooling assembly of heat energy, such as steam reformer.
Described hydrogen fuel cell generates electricity with hydrogen for raw material, provides power for automobile.
This system uses high-performance noble metal catalyst to be used for steam reforming reaction, and is equipped with the change of one-level carbon monoxide middle temperature
Changing device composition miniaturized reactors, after conversion again through metal film separating-purifying hydrogen production device to obtain highly purified hydrogen
Supply fuel cell power generation, uses the heat management system of cooling and heat-exchange apparatus composition can improve small-sized system further
The energy of hydrogen and fuel cell system and raw material service efficiency.
In said system, it is preferable that described reaction tube is alumina tube, its internal diameter is 6-8mm, and external diameter is
10-12mm, this reactor can be made up of, fine and close aluminium oxide tube bundle on the inner and outer wall of reaction tube equably
Deposition has catalyst activity component.
In said system, it is preferable that described carbon monoxide conversion device is fixed bed reactors, and described fixed bed is anti-
It is filled with carbon monoxide transformation catalyst in answering device.
In said system, it is preferable that described membrance separation purified hydrogen device is provided with one or more levels and separates film, described
Separating film is the metal palladium-based composite membrane with alumina tube as substrate.What separates film in actual concrete employing, can be optionally
Depending on, so that the hydrogen after Fen Liing reaches the purity requirement of subsequent fuel cell anode material gas, it is to avoid hydrogen fuel cell
Catalyst poisoning be as the criterion.
In said system, it is preferable that the main body of described hydrogen fuel cell is proton membrane fuel battery or is fired by proton membrane
Material battery and the hybrid battery of energy-storage battery composition.Hydrogen can be set between described chiller and described hydrogen fuel cell
Surge tank, the hydrogen after cooling resupplies fuel cell after can be buffered tank buffering.
In said system, it is preferable that described gas hydrates feedway is gas hydrates storage tank, work
Pressure is 0-6MPa.The water obtained by gas hydrate dissociation can also be used for fuel cell humidifying, and natural gas is hydrated
Thing feedway can further be provided with heat insulating member.
In said system, it is preferable that described chiller is provided with independent hydrogen_cooling pipeline and tail gas cooling tube
Road, separates the tail gas after water and can be used as the fuel of burning heater in steam reformer, and the water being condensed out can fill into sky
So gas hydrate feedway or be used as fuel cell humidifying.
In said system, it is preferable that this system also includes deionized water storage tank and heat exchanger, described deionized water stores up
The entrance of tank connects with chiller, and its outlet connects with hydrogen fuel cell and described heat exchanger respectively, this heat exchanger with
The water vapour pipeline connection of gas hydrates feedway.Deionized water storage tank for store additional deionized water and
The water that chiller is discharged, the water in storage tank can directly fill into the decomposition water bin of gas hydrates feedway,
Also can first vaporize water into as filling into steam reformer or the water vapour of gas hydrates feedway after water vapour
Pipeline；In storage tank, the vaporization of water can be realized by described heat exchanger, the heat of this heat exchanger from heat-producing unit in system,
Cooling assembly, the heat exchanger etc. of chiller of such as steam reformer.
The waste heat that said system produces can be used for heating in winter and/or air conditioner refrigerating in summer in car.
Compared with prior art, present invention have the advantage that and utilize sky in the hydrogen cell automobile that the present invention provides
So the method and system of gas hydrate hydrogen manufacturing in situ is to utilize existing simple gas hydrates supply arrangement, fires at hydrogen
Hydrogen manufacturing in situ, supply hydrogen fuel cell generating is realized on material battery car.
Technical scheme is used to be not required to build substantial amounts of hydrogenation stations and high pressure hydrogen storage tank is installed onboard, investment
Save, expand resistance little.At hydrogen cell automobile hydrogen supply in situ, the waste heat of this system can be used for heating in winter, summer
Refrigeration, therefore need not electricity consumption heating and refrigerating again, and efficiency of energy utilization is higher.
Method technological process provided by the present invention is short, easy of integration, easily realize large-scale application.According to natural gas with
The calorific value calculation of gasoline, 1 standard cubic meter natural gas is equivalent to 1.03 liters of gasoline, and as a example by taxi, every hundred is public
In consume 8 liters of gasoline, need natural gas 8.16 standard cubic meter.If with using technical scheme onboard
Carrying out hydrogen manufacturing in situ, wherein 30% natural gas is used for converting heat supply, and 70% natural gas is used for producing hydrogen from steam conversion, can give birth to
Produce the hydrogen of about 1.73 kilograms, drive a vehicle in terms of 100 kilometers by 1.2 kg hydrogen fuel cell cars, can drive a vehicle about 150
Kilometer, energy efficiency improves 0.5 times.The present invention has significant economic benefit and good adaptability, it is simple to promote
With universal.
Accompanying drawing explanation
Fig. 1 be in embodiment 2-4 in hydrogen cell automobile with the flow chart of gas hydrates in situ hydrogen manufacturing.
Detailed description of the invention
In order to the technical characteristic of the present invention, purpose and beneficial effect are more clearly understood from, the existing skill to the present invention
Art scheme carries out described further below, but it is not intended that to the present invention can the restriction of practical range.
Embodiment 1
Present embodiments provide the system with gas hydrates hydrogen manufacturing in situ, this system in a kind of hydrogen cell automobile
Including:
Gas hydrates feedway, deionized water storage tank, heat exchanger, steam reformer, carbon monodixe conversion
Device, membrance separation purified hydrogen device, chiller, hydrogen gas buffer and hydrogen fuel cell；
Gas hydrates feedway includes gas hydrates bin, heating assembly, gas pipeline, decomposition
Water bin, water vapour pipeline and heat insulating member, and can bear≤the gas pressure of 6MPa；
Steam reformer part includes conversion reactor, product Gas Cooler, burning heater, conversion reactor by
Fine and close aluminium oxide tube bundle composition, on alumina tube inwall, deposition has the active component of steam reforming catalysts, product
Gas Cooler includes preheating assembly and cooling assembly；
Carbon monoxide conversion device is the fixed bed reactors being filled with carbon monoxide transformation catalyst；
The membrane separation assemblies that membrance separation purified hydrogen device uses is the metal palladium-based composite membrane with alumina tube as substrate, including
Entrance pipe, hydrogen pipeline and tail gas pipeline；
Chiller includes that heat exchanger, heat exchanger include cooling line, add pipe line and condensate line, cooling
Pipeline includes the hydrogen pipeline of membrance separation purified hydrogen device, tail gas pipeline, adds pipe line and gas hydrates supply dress
The heating assembly connection put；
Heat exchanger adds pipe line heat exchange for the water and the chiller that are exported by deionized water storage tank, vaporizes water into as water
Steam.
The main body of hydrogen fuel cell be proton membrane fuel battery or by proton membrane fuel battery and energy-storage battery form mixed
Closing battery, it includes hydrogen pipeline, oxygen pipeline, humidification pipeline and discharge pipe line；
The gas pipeline of gas hydrates feedway, water vapour pipeline connect with the preheating assembly of product Gas Cooler
Logical, the outlet of this preheating assembly connects with conversion reactor, the export pipeline of conversion reactor and product Gas Cooler
Cooling assembly connection, the outlet of this cooling assembly connects with carbon monoxide conversion device, carbon monoxide conversion device and film
The entrance pipe connection of separating-purifying hydrogen production device, the tail gas pipeline of membrance separation purified hydrogen device, hydrogen pipeline are respectively with cold
Radiator cooler connects, and the tail gas pipeline of chiller connects with the burning heater of steam reformer, chiller cold
Condensate line connects with the entrance of deionized water storage tank, and the outlet of deionized water storage tank is divided into two branch roads, a branch road with
The humidification pipeline connection of fuel cell, another branch road connects with heat exchanger, heat exchanger and gas hydrates feedway
Water vapour pipeline connection, the hydrogen pipeline of chiller connects with hydrogen gas buffer, hydrogen gas buffer and fuel cell
Hydrogen pipeline connection.
Embodiment 2
Present embodiments provide the method with gas hydrates hydrogen manufacturing in situ, the method in a kind of hydrogen cell automobile
Being that the system provided based on embodiment 1 realizes, its flow process is as it is shown in figure 1, specifically include following steps:
(gas discharge is 22.4Nm for the natural gas exported by gas hydrates feedway and water vapour3/ h, water
Steam flow is 44.8Nm3/ h, H2O/CH4Ratio is 2) after heat exchange, it is warming up to 550 DEG C；
Subsequently into steam reforming reaction device, at Ru-Rh/Al2O3(Ru:Al on catalyst2O3=1.5wt%,
Rh:Al2O3=0.5wt%) carry out steam reforming reaction (CH4Air speed is 500h-1, reflecting mouth pressure is 0.5MPa),
Converting and preparing flow is 106.6Nm3The product gas of/h, product gas outlet temperature about 800 DEG C, gas componant such as table 1
Shown in.
Table 1 product gas gas composition (unit: Nm3/h)
| CO | H2 | H2O | CO2 | CH4 |
| 14.8 | 64.0 | 20.2 | 4.9 | 2.7 |
Product gas is cooled to 350 DEG C after cooling heat transferring, then inputs carbon monoxide conversion device, at carbon monoxide
Transformation catalyst Cr2O3/Co3O4/Fe3O4Reacting on (mass ratio is 10:5:85), reaction pressure is 0.5MPa,
Air speed is 500h-1, transformationreation device output flow is 106.6Nm3The conversion gas of/h, conversion gas temperature is 427 DEG C,
Gas componant is shown in Table 2.
Table 2 conversion gas gas composition (unit: Nm3/h)
| CO | H2 | H2O | CO2 | CH4 |
| 7.6 | 71.2 | 12.0 | 13.1 | 2.7 |
Conversion gas is inputted membrance separation purified hydrogen device, is 63.0Nm through secondary membrane isolated flow3/ h, purity
Be 99.99% hydrogen and flow be 43.6Nm3The tail gas of/h, detects through chromatography, and in hydrogen, CO content is less than
20ppm。
Hydrogen and tail gas are inputted chiller respectively, and the hydrogen being cooled to 40 DEG C supplies hydrogen fuel through hydrogen gas buffer
Cell power generation, the tail gas after cooling enters the burning heater burning of steam reformer；Condensed water after tail gas cooling
Entering deionized water storage tank, the water part in storage tank is used for humidifying fuel cell unstripped gas, and a part is through heat exchanger vapour
After turning to water vapour, the water vapour with gas hydrates feedway mixes.
Embodiment 3
Present embodiments provide a kind of method using gas hydrates hydrogen manufacturing in situ in hydrogen cell automobile, the party
Method is that the system provided based on embodiment 1 realizes, and its flow process is as it is shown in figure 1, specifically include following steps:
(gas discharge is 11.2Nm for the natural gas exported by gas hydrates feedway and water vapour3/ h, water
Steam flow is 33.6Nm3/ h, H2O/CH4Ratio is 3) after heat exchange, it is warming up to 550 DEG C；
Subsequently into steam reforming reaction device at Pt-Ag/Al2O3(Pt:Al on catalyst2O3=1.0wt%,
Ag:Al2O3=0.5wt%) carry out steam reforming reaction (CH4Air speed 5000h-1, reflecting mouth pressure is 1.5MPa),
Converting and preparing flow is 64.6Nm3The product gas of/h, product gas outlet temperature about 850 DEG C, gas componant such as table 3 institute
Show.
Product gas is cooled to 300 DEG C after cooling heat transferring, then inputs carbon monoxide conversion device, at carbon monoxide
Transformation catalyst Cr2O3/Co3O4/Fe3O4Carry out on (mass ratio is 10:10:80) reacting (reaction pressure is 1.4MPa,
Air speed is 2000h-1), transformationreation device output flow is 64.6Nm3The conversion gas of/h, conversion gas temperature is 383 DEG C,
Gas componant is shown in Table 4.
Table 3 product gas gas composition (unit: Nm3/h)
| CO | H2 | H2O | CO2 | CH4 |
| 6.4 | 33.2 | 20.2 | 3.5 | 1.3 |
Table 4 conversion gas gas composition (unit: Nm3/h)
| CO | H2 | H2O | CO2 | CH4 |
| 1.5 | 38.0 | 15.4 | 8.4 | 1.3 |
Conversion gas is inputted membrance separation purified hydrogen device, is 33.0Nm through secondary membrane isolated flow3/ h, purity
Be 99.99% hydrogen and flow be 31.6Nm3The tail gas of/h, detects through chromatography, and in hydrogen, CO content is less than
20ppm。
Hydrogen and tail gas are inputted chiller respectively, and the hydrogen being cooled to 40 DEG C supplies hydrogen fuel through hydrogen gas buffer
Cell power generation, the tail gas after cooling enters the burning heater burning of steam reformer.Condensed water after tail gas cooling
Entering deionized water storage tank, the water part in storage tank is used for humidifying fuel cell unstripped gas, and a part is through heat exchanger vapour
After turning to water vapour, the water vapour with gas hydrates feedway mixes.
Embodiment 4
Present embodiments provide a kind of method using gas hydrates hydrogen manufacturing in situ in hydrogen cell automobile, the party
Method is that the system provided based on embodiment 1 realizes, and its flow process is as it is shown in figure 1, specifically include following steps:
(gas discharge is 11.2Nm for the natural gas exported by gas hydrates feedway and water vapour3/ h, water
Steam flow is 44.8Nm3/ h, H2O/CH4Ratio is 4) after heat exchange, it is warming up to 550 DEG C；
Subsequently into steam reforming reaction device at Pd-Rh/Al2O3(Pd:Al on catalyst2O3=0.4wt%,
Rh:Al2O3=0.1wt%), carry out steam reforming reaction (CH4Air speed 2000h-1, pressure is 1.0MPa), convert system
Obtaining flow is 76.6Nm3The product gas of/h, product gas outlet temperature about 800 DEG C, gas componant is as shown in table 5.
Table 5 product gas gas composition (unit: Nm3/h)
| CO | H2 | H2O | CO2 | CH4 |
| 5.5 | 35.7 | 29.7 | 4.8 | 0.9 |
It is cooled to 350 DEG C after the cooled device heat exchange of product gas, then inputs carbon monoxide conversion device, at carbon monoxide
Transformation catalyst Cr2O3/Co3O4/Fe3O4Reacting on (mass ratio is 5:10:85), reaction pressure is 1.0MPa,
Transformationreation device output 76.6Nm3The conversion gas of/h, conversion gas temperature is 405 DEG C, and gas componant is shown in Table 6.
Conversion gas is inputted membrance separation purified hydrogen device, is 34.0Nm through secondary membrane isolated flow3/ h purity is
The hydrogen of 99.99% and flow are 42.6Nm3The tail gas of/h, detects through chromatography, and in hydrogen, CO content is less than
20ppm。
Table 6 conversion gas gas composition (unit: Nm3/h)
| CO | H2 | H2O | CO2 | CH4 |
| 1.4 | 39.9 | 25.5 | 8.9 | 0.9 |
Hydrogen and tail gas are inputted chiller respectively, and the hydrogen being cooled to 40 DEG C supplies hydrogen fuel through hydrogen gas buffer
Cell power generation, the tail gas after cooling enters the burning heater burning of steam reformer.Condensed water after tail gas cooling
Entering deionized water storage tank, the water part in storage tank is used for humidifying fuel cell unstripped gas, and a part is through heat exchanger vapour
After turning to water vapour, the water vapour with gas hydrates feedway mixes.
Claims (12)
1. one kind in hydrogen cell automobile by the system of gas hydrates in situ hydrogen manufacturing, it is characterised in that this is
System includes:
Gas hydrates feedway, steam reformer, carbon monoxide conversion device, membrance separation purified hydrogen device,
Chiller and hydrogen fuel cell；
Described gas hydrates feedway connects with described steam reformer, described steam reformer and described
Carbonoxide converting means connects, and described carbon monoxide conversion device connects with described membrance separation purified hydrogen device, and described film divides
Connecting with described chiller from purified hydrogen device, described chiller connects with described hydrogen fuel cell；
Described gas hydrates feedway is provided with gas hydrates bin, heating assembly, gas pipeline, divides
Solve water bin and water vapour pipeline；
Described steam reformer includes preheating assembly, cooling assembly, burning heater and reactor, and described reactor is
Calandria type fixed bed reactor, on the reaction tube of this calandria type fixed bed reactor, deposition has the activity of steam reforming catalysts
Component, the entrance of described preheating assembly is respectively with the gas pipeline of gas hydrates feedway and water vapour pipeline even
Logical, the outlet of preheating assembly connects with the entrance of reactor；The entrance of described cooling assembly and the outlet of reactor,
The described outlet of cooling assembly connects with the entrance of carbon monoxide conversion device, the fuel conduit of described burning heater and confession
Device of air and/or chiller connection.
2. the system as claimed in claim 1, it is characterised in that described reaction tube is alumina tube, its internal diameter is
6-8mm, external diameter is 10-12mm；Described carbon monoxide conversion device is fixed bed reactors, described fixed bed reactors
Inside it is filled with carbon monoxide transformation catalyst.
3. system as claimed in claim 2, it is characterised in that the steam reforming catalyst of deposition on described alumina tube
The active component of agent includes the combination of one or more in Pt, Pd, Rh, Ag and Ru；Quality with alumina tube
Meter, active component load capacity on alumina tube is 0.5-2.0wt%.
4. system as claimed in claim 2, it is characterised in that by weight percentage, described carbon monodixe conversion
Catalyst has following components: 5-10wt%Cr2O3, 5-10wt%Co3O4, remaining be ferrum oxide.
5. the system as claimed in claim 1, it is characterised in that described membrance separation purified hydrogen device be provided with one-level or
Multiple stage separation film, described separation film is the metal palladium-based composite membrane with alumina tube as substrate；Described chiller includes heat friendship
Parallel operation.
6. the system as described in claim 1-5 any one, it is characterised in that the main body of described hydrogen fuel cell is
Proton membrane fuel battery or the hybrid battery being made up of proton membrane fuel battery and energy-storage battery.
7. the system as described in claim 1-5 any one, it is characterised in that described gas hydrates supply dress
Being set to gas hydrates storage tank, operating pressure is 0-6MPa.
8. system as claimed in claim 6, it is characterised in that described gas hydrates feedway is natural gas
Hydrate storage tank, operating pressure is 0-6MPa.
9. the system as described in claim 1-5 any one, it is characterised in that this system also includes that deionized water stores up
Tank and heat exchanger, the entrance of described deionized water storage tank connects with chiller, its outlet respectively with hydrogen fuel cell and institute
State heat exchanger connection, this heat exchanger and the water vapour pipeline connection of gas hydrates feedway.
10. system as claimed in claim 6, it is characterised in that this system also includes deionized water storage tank and heat exchanger,
The entrance of described deionized water storage tank connects with chiller, and its outlet connects with hydrogen fuel cell and described heat exchanger respectively
Logical, this heat exchanger and the water vapour pipeline connection of gas hydrates feedway.
11. systems as claimed in claim 7, it is characterised in that this system also includes deionized water storage tank and heat exchanger,
The entrance of described deionized water storage tank connects with chiller, and its outlet connects with hydrogen fuel cell and described heat exchanger respectively
Logical, this heat exchanger and the water vapour pipeline connection of gas hydrates feedway.
12. systems as claimed in claim 8, it is characterised in that this system also includes deionized water storage tank and heat exchanger,
The entrance of described deionized water storage tank connects with chiller, and its outlet connects with hydrogen fuel cell and described heat exchanger respectively
Logical, this heat exchanger and the water vapour pipeline connection of gas hydrates feedway.
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| CN107946615A (en) * | 2017-12-11 | 2018-04-20 | 新源动力股份有限公司 | A kind of method and hydrogen-feeding system of fuel cell car hydrogen supply |
| CN111689469B (en) * | 2019-03-15 | 2023-05-26 | 中国石油化工股份有限公司 | Process for preparing high-purity hydrogen by adopting palladium alloy membrane purification |
| CN114142061B (en) * | 2021-12-01 | 2024-03-08 | 上海船舶研究设计院（中国船舶工业集团公司第六0四研究院） | Shipboard hydrogen fuel preparation system and hydrogen production method thereof |
| CN114976156B (en) * | 2022-04-02 | 2024-01-30 | 河南理工大学 | Methane hydrate decomposition-electrolysis fuel cell |
| CN114988364B (en) * | 2022-06-13 | 2023-05-12 | 重庆科技学院 | Power generation system based on natural gas hydrogen production and fuel cell technology |
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| CN201402883Y (en) * | 2009-04-30 | 2010-02-10 | 永泰电子（东莞）有限公司 | Electrical connector and metal shell thereon |
| CN102173381B (en) * | 2011-02-28 | 2012-08-08 | 四川亚联高科技股份有限公司 | Method for preparing hydrogen with natural gas as raw material |
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| CN102173381B (en) * | 2011-02-28 | 2012-08-08 | 四川亚联高科技股份有限公司 | Method for preparing hydrogen with natural gas as raw material |
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