CN105762389A

CN105762389A - Carbon dioxide circulating type water-hydrogen power generation system

Info

Publication number: CN105762389A
Application number: CN201610220762.1A
Authority: CN
Inventors: 向华
Original assignee: Shanghai Hejide Dynamic Hydrogen Machine Co Ltd
Current assignee: Shanghai Hejide Dynamic Hydrogen Machine Co Ltd
Priority date: 2016-04-11
Filing date: 2016-04-11
Publication date: 2016-07-13

Abstract

The invention discloses a carbon dioxide circulating type water-hydrogen power generation system. The carbon dioxide circulating type water-hydrogen power generation system comprises a methanol hydrogen production system, a hydrogen power generation system and methanol preparation equipment, wherein the methanol hydrogen production system is connected with the hydrogen power generation system; the hydrogen power generation system is connected with the methanol preparation equipment; the methanol hydrogen production system is used for reforming methanol steam to prepare hydrogen and the hydrogen passes through a membrane separation device plated with a palladium-silver alloy to obtain high-purity hydrogen which is then used for generating power through the hydrogen power generation system; the methanol preparation equipment comprises a hydrogen conveying device, a second conveying device and a synthesis reactor; the second conveying device is a carbon dioxide conveying device or/and a carbon monoxide conveying device; the hydrogen conveying device and the second conveying device are connected with the synthesis reactor, respectively; and hydrogen in the synthesis reactor is reacted with carbon dioxide or carbon monoxide to generate methanol and water. The carbon dioxide circulating type water-hydrogen power generation system disclosed by the invention can be used for preparing methanol needed by the power generation system and is capable of avoiding the emission of carbon dioxide.

Description

A kind of carbon dioxide recycle formula water hydrogen electricity generation system

Technical field

The invention belongs to technical field of power generation, relate to a kind of electricity generation system, particularly relate to a kind of carbon dioxide recycle formula water hydrogen electricity generation system.

Background technology

Methanol (Methanol, CH₄O) the simplest saturated monohydroxy alcohol of architecture, molecular weight 32.04, boiling point 64.7 DEG C.Because finding first in dry distilling timber, therefore also known as " another name for " or " another name for ", it is colourless have the volatile liquid of alcohol smell.In recent years, the applicant has applied for that some utilize the patent of methanol-water reformation hydrogen production successively.

In numerous new forms of energy, Hydrogen Energy will become the 21 century optimal energy.This is because, when burning the coal of identical weight, gasoline and hydrogen, the energy that hydrogen produces is maximum, and the product of its burning is water, it does not have lime-ash and waste gas, does not pollute the environment；And coal and oil combustion generate is carbon dioxide and sulfur dioxide, greenhouse effect and acid rain can be produced respectively.Coal and reserves are limited, and hydrogen is mainly stored in water, and after burning, unique product is also water, can produce hydrogen continuously, be finished never.

Hydrogen is a kind of colourless gas.One gram of Hydrogen Energy of burning discharges your heat of 142 kilojoules, is 3 times of gasoline caloric value.The weight of hydrogen is particularly lightweight, and it is all light more than gasoline, natural gas, kerosene, thus carries, transports conveniently, is the most suitable fuel of the high-speed flight vehicles such as space flight, aviation.Hydrogen can burn in oxygen, and the temperature of hydrogen flame may be up to 2500 DEG C, thus the conventional hydrogen cutting of people or welding ferrous materials.

In the Nature, the distribution of hydrogen is very extensive.Water is exactly big " warehouse " of hydrogen, wherein contains the hydrogen of 11%.There is the hydrogen of 1.5% earth Rio；All contain hydrogen in oil, coal, natural gas, animal and plant body etc..The main body of hydrogen is to exist with the form of compound water, and earth surface about 70% is covered by water, and moisture storage capacity is very big, accordingly, it can be said that hydrogen is the energy of " inexhaustible, nexhaustible ".If can with suitable method preparing hydrogen from water, then hydrogen also will be the comparatively inexpensive energy of a kind of price.

Having many uses of hydrogen, the suitability is strong.It can not only be used as fuel, and metal hydride has the function that chemical energy, heat energy and mechanical energy are changed mutually.Such as, hydrogen storage metal has inhales hydrogen heat release and the ability putting hydrogen of absorbing heat, and can be got up by heat storage, use as heating in room and air-conditioning.

Hydrogen, as gaseous fuel, is first used on automobile.In May, 1976, the U.S. develops a kind of automobile making fuel with hydrogen；Later, Japan also succeeded in developing a kind of automobile being fuel with liquified hydrogen；In the latter stage seventies, hydrogen has been tested by the Mercedes of front Germany, and they have only used five kg of hydrogen, just makes running car 110 kilometers.

With hydrogen as motor vehicle fuel, not only totally, easily start at low temperatures, and the corrosiveness of electromotor is little, the service life of electromotor can be extended.Due to hydrogen and air can Homogeneous phase mixing, carburator used on general automobile can be saved completely, thus the structure of existing automobile can be simplified.More interestingly, if in the oil add 4% hydrogen.Use it as automobile engine fuel, so that it may fuel-economizing 40%, and without petrol engine being done great improvement.

Hydrogen easily becomes liquid under certain pressure and temperature, thus it is all very convenient with iron flask car, on-highway tractor or ship transportation.The hydrogen of liquid both can be used as the fuel of automobile, aircraft, it is possible to as the fuel of rocket, guided missile.The U.S. is flown to the Apollo Personnel investigation Program of the moon " Long March carrier rocket that number spacecraft and China launch a man-made satellite., all make fuel with liquified hydrogen.

It addition, use hydrogen hydrogen fuel cell Hydrogen Energy can also be directly translated into electric energy, make utilizing of Hydrogen Energy more convenient.At present, this fuel cell is used in spacecraft and submarine, and effect is pretty good.Certainly, due to relatively costly, also it is difficult to commonly use for the moment.

Now the annual production of hydrogen is about 36,000,000 tons in the world, is wherein mostly and produces from oil, coal and natural gas, and this must consume fossil fuel natively very in short supply；The hydrogen separately having 4% is to produce by the method for electrolysis water, but the electric energy consumed is too many, does not calculate very much, and therefore, people are trying to explore research hydrogen manufacturing new method.And the energy consumption in Chemical Manufacture can be reduced with methanol, water reformation hydrogen production and reduce cost, it is expected to substitute the technique of " water electrolysis hydrogen production " that be referred to as electricity-eating tiger, utilizes advanced methanol vapor to reform--pressure swing adsorption making pure hydrogen and rich in CO₂Mixing gas, through further post processing, hydrogen and carbon dioxide gas can be obtained simultaneously.

By catalyst, under the effect of catalyst, there is the transformationreation of methanol decomposition reaction and carbon monoxide, generate hydrogen and carbon dioxide in methanol and steam, this is the gas solid catalytic reaction system of component more than, many reactions under certain temperature, pressure condition.Reactional equation is as follows:

CH₃OH→CO+2H₂(1)

H₂O+CO→CO₂+H₂(2)

CH₃OH+H₂O→CO₂+3H₂(3)

The H that reforming reaction generates₂And CO₂, then through palladium membrance separation by H₂And CO₂Separate, obtain high-purity hydrogen.The power consumption of pressure swing adsorption method is high, equipment is big, and is not suitable for small-scale hydrogen and prepares.

Additionally, currently existing scheme needs discharge carbon dioxide (hydrogen gas generation that utilization prepares) when preparing hydrogen, the material benzenemethanol preparing hydrogen then needs other purchase.

In view of this, nowadays in the urgent need to designing a kind of new hydrogen gas generating system, in order to overcome the drawbacks described above that existing hydrogen electricity generation system exists.

Summary of the invention

The technical problem to be solved is: provides a kind of carbon dioxide recycle formula water hydrogen electricity generation system, can make the methanol needed for electricity generation system by oneself, and avoid the discharge of carbon dioxide.

For solving above-mentioned technical problem, the present invention adopts the following technical scheme that

A kind of carbon dioxide recycle formula water hydrogen electricity generation system, described carbon dioxide recycle formula water hydrogen electricity generation system includes: hydrogen production by methanol system, hydrogen gas generating system, methanol Preparation equipment, hydrogen production by methanol system is connected with hydrogen gas generating system, and hydrogen gas generating system is connected with methanol Preparation equipment；The electric energy work that methanol Preparation equipment is sent by hydrogen gas generating system；

Described hydrogen production by methanol system includes hydrogen manufacturing subsystem, air pressure adjustment subsystem, Collection utilization subsystem, and hydrogen manufacturing subsystem, air pressure adjustment subsystem, hydrogen gas generating system, Collection utilization subsystem are sequentially connected with；

Described hydrogen manufacturing subsystem utilizes methanol-water to prepare hydrogen, and described hydrogen manufacturing subsystem includes solid hydrogen and stores container, stores container, raw material conveying device, device for rapidly starting, hydrogen producer, membrane separation device；

Described storage container includes: driving mechanism that container, the space mechanism being arranged in container are connected with space mechanism, control module, induction module；Container is at least divided into two spaces by described space mechanism；In two spaces, a placing response liquid, opposite side arranges the carbon dioxide of hydrogen gas generating system release, the liquid then compressed or solid-state；Control module and connect driving mechanism, induction module respectively；Described driving mechanism includes motor, and induction module includes pressure transducer or/and liquid level sensor；Described induction module, in order to sense the amount of reaction liquid in container, senses the amount of the carbon dioxide of hydrogen gas generating system release, the liquid then compressed or solid-state simultaneously；And sensed data is sent to controlling module；The Data Control driving mechanism that described control module senses according to the induction module action to space mechanism；When the liquid stored in container reduces or carbon dioxide increases up to impose a condition, driving mechanism drives space mechanism action, reduces the volume of reaction liquid, increases the volume of carbon dioxide；Described storage container also includes liquefying plant or/and solidification equipment, by the co 2 liquefaction collected or/and solidify；

Described hydrogen producer includes heat exchanger, vaporizer, reformer chamber；Membrane separation device is arranged in separation chamber, and separation chamber is arranged at the inside of reformer chamber；Described solid hydrogen stores container, storage container is connected with hydrogen producer respectively；Store the first alcohol and water storing liquid in container；

Described device for rapidly starting provides for hydrogen producer and starts the energy；Described device for rapidly starting includes the first startup device, the second startup device；Described first starts device includes the first heating arrangements, the first gasification pipe, and the internal diameter of the first gasification pipe is 1～2mm, and the first gasification pipe is closely wound on the first heating arrangements；One end of described first gasification pipe connects storage container, is sent in the first gasification pipe by methanol by raw material conveying device；The other end of the first gasification pipe exports vaporized methanol, then by ignition mechanism ignition；Or, the other end of the first gasification pipe exports vaporized methanol, and the methanol temperature of output reaches self-ignition point, and methanol is direct spontaneous combustion after exporting from the first gasification pipe；Described second starts device includes the second gasification pipe, the main body of the second gasification pipe is arranged at described reformer chamber, first gasification pipe is or/and the methanol of the second gasification pipe output heats the second gasification pipe while being reformer chamber heating, by the methanol gasifying in the second gasification pipe；Described reformer chamber inwall is provided with and adds pipe line, adds and is placed with catalyst in pipe line；Described device for rapidly starting by heat described in add pipe line attach most importance to whole room heating；After described hydrogen generating system starts, hydrogen generating system is provided by the hydrogen that hydrogen producer prepares and runs the required energy；

The initial start energy of described device for rapidly starting is that some solar energys start module, and solar energy starts solar panel that module includes being sequentially connected with, solar energy-electric energy change-over circuit, solaode；Solar energy starts module provides electric energy for the first heating arrangements；Or, the initial start energy of described device for rapidly starting is manual generator, and the electric energy sent is stored in battery by manual generator；

Described catalyst includes the oxide of Pt, the oxide of Pd, the oxide of Cu, the oxide of Fe, the oxide of Zn, rare-earth oxide, transition metal oxide；Wherein, precious metals pt content accounts for the 0.6%～1.8% of catalyst gross mass, Pd content accounts for the 1.1%～4% of catalyst gross mass, the oxide of Cu accounts for the 6%～12% of catalyst gross mass, the oxide of Fe accounts for the 3%～8% of catalyst gross mass, the oxide of Zn accounts for the 8%～20% of catalyst gross mass, and rare-earth oxide accounts for the 6%～40% of catalyst gross mass, and all the other are transition metal oxide；

Or, described catalyst is copper-based catalysts, including material and mass fraction thereof is: the Al of ZrO, 55-80 part of ZnO, 0.5-3 part of CuO, 3-18 part of 3-17 part₂O₃, the CeO of 1-3 part₂, the La of 1-3 part₂O₃；

Described solid hydrogen stores and stores solid hydrogen in container, and when hydrogen generating system starts, by gasifying, solid hydrogen is converted to gaseous hydrogen by module, and gaseous hydrogen passes through combustion heat release, provides for hydrogen producer and starts heat energy, as the startup energy of hydrogen producer；

First alcohol and water in described storage container is delivered to heat exchanger heat exchange by raw material conveying device, enters vaporizer gasification after heat exchange；Methanol vapor and steam after gasification enter reformer chamber, and it is 300 DEG C～420 DEG C that reformer chamber is provided with catalyst, reformer chamber bottom and middle portion temperature；The temperature on described reformer chamber top is 400 DEG C～570 DEG C；Reformer chamber is connected by connecting line with separation chamber, all or part of top being arranged at reformer chamber of connecting line, and the high temperature that can pass through reformer chamber top continues the heating gas from reformer chamber output；Described connecting line is as the buffering between reformer chamber and separation chamber so that identical or close with the temperature of separation chamber from the temperature of the gas of reformer chamber output；Temperature in described separation chamber is set as 350 DEG C～570 DEG C；It is provided with membrane separator in separation chamber, obtains hydrogen from the aerogenesis end of membrane separator；

Described raw material conveying device provides power, by the feedstock transportation in storage container to hydrogen producer；Described raw material conveying device provides the pressure of 0.15～5MPa to raw material so that the hydrogen that hydrogen producer prepares has enough pressure；

After described hydrogen producer starts hydrogen manufacturing, the hydrogen partial that hydrogen producer prepares is or/and residual air is run by the maintenance hydrogen producer that burns；

The hydrogen that described hydrogen producer prepares is delivered to membrane separation device and is easily separated, for the difference of inside and outside pressure of membrane separation device of separating hydrogen gas be more than or equal to 0.7MPa；Described membrane separation device is the membrane separation device at porous ceramic surface Vacuum Deposition palladium-silver, and film plating layer is palladium-silver, and the mass percent palladium of palladium-silver accounts for 75%～78%, and silver accounts for 22%～25%；

Described hydrogen manufacturing subsystem by prepared hydrogen by transfer conduit real-time Transmission to hydrogen gas generating system；Described transfer conduit is provided with air pressure adjustment subsystem, for adjusting the air pressure in transfer conduit；Described hydrogen gas generating system utilizes the hydrogen gas generation that hydrogen manufacturing subsystem prepares；

Described air pressure adjustment subsystem includes microprocessor, gas pressure sensor, valve positioner, air outlet valve, outlet pipe；Described gas pressure sensor is arranged in transfer conduit, in order to sense the barometric information in transfer conduit, and sends the barometric information of sensing to microprocessor；This barometric information received from gas pressure sensor is compared by described microprocessor with setting threshold interval；When the pressure data received is higher than the maximum setting threshold interval, microprocessor controls valve positioner and opens the air outlet valve setting time, air pressure in transfer conduit is made to be in set point, one end of outlet pipe connects air outlet valve simultaneously, the other end connects described hydrogen manufacturing subsystem, is that the firing equipment that needs of hydrogen manufacturing subsystem is heated by burning；When the pressure data received is lower than the minima setting threshold interval, microprocessor controls described hydrogen manufacturing subsystem and accelerates the transporting velocity of raw material；

Described Collection utilization subsystem connects the Vent passageway of hydrogen gas generating system, hydrogen, oxygen gas and water is collected respectively from expellant gas, utilize the hydrogen collected, oxygen for hydrogen manufacturing subsystem or/and hydrogen gas generating system, the water collected is as the raw material of hydrogen manufacturing subsystem, thus recycling；

Described Collection utilization subsystem includes hydrogen/oxygen separator, hydrogen water separator, hydrogen check-valves, oxygen water separator, oxygen check valve, by hydrogen and oxygen separation, is then separated from water by hydrogen respectively, oxygen is separated from water；

Described hydrogen producer also includes electric energy estimation block, hydrogen prepares detection module, electric energy memory module；The electric energy that when whether the electric energy that described electric energy estimation block sends in real time in order to estimate hydrogen gas generation device can meet reformation, separation, needs consume；If it is satisfied, then closedown device for rapidly starting；

Whether hydrogen prepares the hydrogen that detection module prepared in real time for detecting hydrogen producer stable；If hydrogen prepared by hydrogen producer is unstable, then controls device for rapidly starting and be again started up, and the electric energy obtained is partially stored in electric energy memory module, use when electric energy is not enough to the consumption providing hydrogen producer；

Described hydrogen gas generating system is fuel cell system, and fuel cell system includes: gas supply device, pile；Described gas supply device utilizes the gas of compression as power, and automatic transport is to pile；Described pile includes some sub-fuel cell modules, and each sub-fuel cell module includes at least one super capacitor；

Described fuel cell system also includes air intake conduit, outlet pipe；The gas of described compression is mainly oxygen；Air enters pile with oxygen after mixing container mixing；

Described fuel cell system also includes gas regulating system；Described gas regulating system includes valve regulated and controls device, and oxygen content sensor is or/and compress gas compression ratio sensor；

Described oxygen content sensor is in order to sense the air of mixing and the content of oxygen in oxygen in mixing container, and the data sensed is sent to valve regulated control device；

Described compression gas compression ratio sensor is in order to sense the compression ratio of compressed oxygen, and the data sensed is sent to valve regulated control device；

Described valve regulated controls device according to oxygen content sensor or/and the sensing result of compression gas compression ratio sensor regulates oxygen delivery valve door, air entrainment valve door, controls the conveying ratio of compressed oxygen, air；Mixing gas is pushed to pile reaction by the power that compressed oxygen produces after entering mixing container；

Described fuel cell system also includes humidification system, and humidification system includes humidity exchanging container, humidity exchange pipeline, and humidity exchange pipeline is a part for air intake conduit；After reaction, gas is delivered to humidity exchanging container by outlet pipe,

The material of described humidity exchange pipeline is only permeable airtight so that after reaction, gas and natural air carry out humidity exchange, and cannot circulate between gas.

Described methanol Preparation equipment includes: nitrogen gas conveying device, hydrogen conveyor, carbon dioxide conveyer device, the first blender, the second gaseous mixture, micro fixed-bed reactor, counterbalance valve, synthesis reactor, alcohol-water separation device, chromatograph, methanol solution gasifying device, methanol collect container, main control module；Described carbon dioxide conveyer device connects the side of described storage container collection carbon dioxide；The methanol prepared is delivered to the methanol-water mixed liquor side storing container；

Described nitrogen gas conveying device includes nitrogen storage container, the first transfer pipeline, and the first transfer pipeline is provided with the first stop valve, the first mass flowmenter；

Described carbon dioxide conveyer device includes carbon dioxide storage container, the second transfer pipeline, and the second transfer pipeline is provided with the second stop valve, the second mass flowmenter；

Described hydrogen conveyor includes hydrogen storage vessel, the 3rd transfer pipeline, the 4th transfer pipeline, and the 3rd transfer pipeline is provided with the 3rd stop valve, the 3rd mass flowmenter, and the 4th transfer pipeline is provided with the 4th stop valve, the 4th mass flowmenter；

Described hydrogen storage vessel is connected by the 3rd transfer pipeline and the first transfer pipeline, and the 3rd transfer pipeline and the first transfer pipeline are intersected in one first three-way valve；

Described hydrogen storage vessel is connected by the 4th transfer pipeline and the second transfer pipeline, and the 4th transfer pipeline and the second transfer pipeline are intersected in one first cross valve；

Described first three-way valve and the first blender connect, and the other end of the first blender and the second three-way valve connect；Second three-way valve connects micro fixed-bed reactor by the 5th transfer pipeline, and the 5th transfer pipeline is provided with the 5th mass flowmenter, pressure gage；

The other end of described micro fixed-bed reactor connects the 4th three-way valve, and the 4th three-way valve is also connected with counterbalance valve, and the other end of counterbalance valve connects one second cross valve；

Described first cross valve and the second blender connect, and the other end of the second blender and the 3rd three-way valve connect；Alcohol-water separation device, the second three-way valve connect the 3rd three-way valve, and alcohol-water separation device, methanol solution gasifying device, chromatograph connect the second cross valve；Methanol solution gasifying device is collected container with methanol and is connected；

Described master control module controls all parts action, first control high pure nitrogen and high-purity hydrogen to be emptied by beds after the first blender mixing with the ratio set, treat that catalyst reduction completes the gaseous mixture that rear cutout ventilation body is hydrogen and carbon dioxide, gas boosts to certain pressure by beds through counterbalance valve and isolates Methanol product and water then through alcohol-water separation device, and unreacted gas continues through reactor cycles reaction after unstripped gas supplements.

A kind of carbon dioxide recycle formula water hydrogen electricity generation system, described carbon dioxide recycle formula water hydrogen electricity generation system includes: hydrogen production by methanol system, hydrogen gas generating system, methanol Preparation equipment, hydrogen production by methanol system is connected with hydrogen gas generating system, and hydrogen gas generating system is connected with methanol Preparation equipment；

Described hydrogen production by methanol system utilizes preparing hydrogen by reforming methanol-water steam, and hydrogen obtains highly purified hydrogen by being coated with the membrane separation device of palladium-silver, and the hydrogen of acquisition is generated electricity by hydrogen gas generating system；

Described methanol Preparation equipment includes: hydrogen conveyor, the second conveyer device, synthesis reactor；Described second conveyer device is carbon dioxide conveyer device or/and carbon monoxide conveyer device；Described hydrogen conveyor, the second conveyer device are connected with synthesis reactor respectively；In described synthesis reactor, hydrogen and carbon dioxide or reaction of carbon monoxide, generate methanol and water.

As a preferred embodiment of the present invention, described hydrogen production by methanol system includes storing container；The middle part of described storage container is provided with dividing plate, and the side of dividing plate arranges reaction liquid, and opposite side arranges the carbon dioxide of hydrogen gas generating system release, the liquid then compressed or solid-state；Dividing plate is connected to pushing mechanism, and when the liquid stored in container reduces or carbon dioxide increases up to impose a condition, pushing mechanism drives dividing plate action, reduces the volume of storage reaction liquid regions, increases the volume in storage carbon dioxide region.

As a preferred embodiment of the present invention, described storage container also includes controlling module, induction module；Described driving mechanism includes motor, and induction module includes pressure transducer or/and liquid level sensor；Described induction module, in order to sense the amount of reaction liquid in container, senses the amount of the carbon dioxide of hydrogen gas generating system release, the liquid then compressed or solid-state simultaneously；And sensed data is sent to controlling module；The Data Control driving mechanism that described control module senses according to the induction module action to space mechanism；When liquid in liquid storage container reduces or carbon dioxide increases up to impose a condition, driving mechanism drives space mechanism action, reduces the volume of reaction liquid, increases the volume of carbon dioxide；Described storage device also includes liquefying plant or/and solidification equipment, by the co 2 liquefaction collected or/and solidify.

As a preferred embodiment of the present invention, described hydrogen production by methanol system includes hydrogen manufacturing subsystem, air pressure adjustment subsystem, Collection utilization subsystem, and hydrogen manufacturing subsystem, air pressure adjustment subsystem, hydrogen gas generating system, Collection utilization subsystem are sequentially connected with；

As a preferred embodiment of the present invention, the initial start energy of described device for rapidly starting is that some solar energys start module, and solar energy starts solar panel that module includes being sequentially connected with, solar energy-electric energy change-over circuit, solaode；Solar energy starts module provides electric energy for the first heating arrangements；Or, the initial start energy of described device for rapidly starting is manual generator, and the electric energy sent is stored in battery by manual generator.

As a preferred embodiment of the present invention, described catalyst includes the oxide of Pt, the oxide of Pd, the oxide of Cu, the oxide of Fe, the oxide of Zn, rare-earth oxide, transition metal oxide；Wherein, precious metals pt content accounts for the 0.6%～1.8% of catalyst gross mass, Pd content accounts for the 1.1%～4% of catalyst gross mass, the oxide of Cu accounts for the 6%～12% of catalyst gross mass, the oxide of Fe accounts for the 3%～8% of catalyst gross mass, the oxide of Zn accounts for the 8%～20% of catalyst gross mass, and rare-earth oxide accounts for the 6%～40% of catalyst gross mass, and all the other are transition metal oxide；

Or, described catalyst is copper-based catalysts, including material and mass fraction thereof is: the Al of ZrO, 55-80 part of ZnO, 0.5-3 part of CuO, 3-18 part of 3-17 part₂O₃, the CeO of 1-3 part₂, the La of 1-3 part₂O₃。

As a preferred embodiment of the present invention, described methanol Preparation equipment includes: nitrogen gas conveying device, hydrogen conveyor, carbon dioxide conveyer device, the first blender, the second gaseous mixture, micro fixed-bed reactor, counterbalance valve, synthesis reactor, alcohol-water separation device, chromatograph, methanol solution gasifying device, methanol collect container, main control module；Described carbon dioxide conveyer device connects the side of described storage container collection carbon dioxide；The methanol prepared is delivered to the methanol-water mixed liquor side storing container；

The beneficial effects of the present invention is: the carbon dioxide recycle formula water hydrogen electricity generation system that the present invention proposes, the methanol needed for electricity generation system can be made by oneself, and avoid the discharge of carbon dioxide.

Accompanying drawing explanation

Fig. 1 is the composition schematic diagram of carbon dioxide recycle formula water hydrogen electricity generation system of the present invention.

Fig. 2 is the composition schematic diagram of hydrogen production by methanol system in present system.

Fig. 3 is the structural representation of device for rapidly starting in hydrogen producer

Fig. 4 is hydrogen producer and the structural representation adding pipe line thereof.

Fig. 5 is the composition schematic diagram of the hydrogen producer being provided with relief valve.

Fig. 6 is the schematic diagram under the another kind of state of the hydrogen producer being provided with relief valve.

Fig. 7 is the composition schematic diagram of fuel cell system in present system.

Fig. 8 is the structural representation of liquid container.

Fig. 9 is the composition schematic diagram of methanol Preparation equipment in present system.

Detailed description of the invention

The preferred embodiments of the present invention are described in detail below in conjunction with accompanying drawing.

Embodiment one

Refer to Fig. 1, present invention is disclosed a kind of water hydrogen electricity generation system, described water hydrogen electricity generation system includes: hydrogen production by methanol system, hydrogen gas generating system, methanol Preparation equipment, and hydrogen production by methanol system is connected with hydrogen gas generating system, and hydrogen gas generating system is connected with methanol Preparation equipment；The electric energy work that methanol Preparation equipment is sent by hydrogen gas generating system.

In the present embodiment, referring to Fig. 2, hydrogen production by methanol system is small portable hydrogen producer, including: liquid container 10, raw material conveying device 50, device for rapidly starting 40, device for producing hydrogen 20, membrane separation device 30, hydrogen delivery tube road 60.

Referring to Fig. 8, the middle part of liquid container is provided with dividing plate 101, and the side of dividing plate 101 arranges reaction liquid, and opposite side arranges the carbon dioxide of hydrogen gas generating system release, the liquid then compressed or solid-state.Dividing plate 101 is connected to driving mechanism, and when the liquid stored in container reduces or carbon dioxide increases up to impose a condition, driving mechanism drives dividing plate action, reduces the volume of storage reaction liquid regions, increases the volume in storage carbon dioxide region.So while preparing hydrogen, can collecting the carbon dioxide of release, reduce the discharge of carbon dioxide, the carbon dioxide of collection is also used as the raw material of subsequent handling.The two ends of dividing plate 101 are arranged in chute 102, can slide along chute 102.

Described liquid container can also include controlling module, induction module；Described driving mechanism includes motor, and induction module includes pressure transducer or/and liquid level sensor；Described induction module, in order to sense the amount of reaction liquid in container, senses the amount of the carbon dioxide of hydrogen gas generating system release, the liquid then compressed or solid-state simultaneously；And sensed data is sent to controlling module；The Data Control driving mechanism that described control module senses according to the induction module action to space mechanism；When liquid in liquid storage container reduces or carbon dioxide increases up to impose a condition, driving mechanism drives space mechanism action, reduces the volume of reaction liquid, increases the volume of carbon dioxide.Described liquid container also can include liquefying plant or/and solidification equipment, by the co 2 liquefaction collected or/and solidify.

As it is shown on figure 3, described device for rapidly starting 40 includes housing 41, heating arrangements 42, gasification pipe 43, the internal diameter of gasification pipe 43 is 1～2mm, and gasification pipe 43 is wound on heating arrangements 42；Described heating arrangements can be electrically heated rod, utilizes alternating current or accumulator, aneroid battery.

One end of described gasification pipe 43 connects liquid container 10, is sent into by methanol in gasification pipe 43；The other end of gasification pipe 43 exports vaporized methanol, then by ignition mechanism ignition；Or, the other end of gasification pipe 43 exports vaporized methanol, and the methanol temperature of output reaches self-ignition point, and methanol is direct spontaneous combustion after exporting from gasification pipe 43；Described device for rapidly starting 40 is that device for producing hydrogen (in other words whole hydrogen producer) provides the startup energy.

Referring to Fig. 4, in order to improve the firing rate of device for producing hydrogen, the reformer chamber inwall at described device for producing hydrogen 20 is provided with and adds pipe line 21, adds and is placed with catalyst (as can by heating and temperature control at 380 DEG C～480 DEG C) in pipe line 21；Described device for rapidly starting 40 adds pipe line 21 for reformer chamber heating described in heating, it is possible to improve the efficiency of heating surface.

As shown in Figure 2, device for producing hydrogen 20 can also arrange the second startup device 70, described second starts device 70 includes the second gasification pipe, and the main body of the second gasification pipe is arranged at reformer chamber, and the second gasification pipe is reformer chamber heating (can also be the heating of other unit of hydrogen producer).First gasification pipe is or/and the methanol of the second gasification pipe output heats the second gasification pipe while being reformer chamber heating, by the methanol gasifying in the second gasification pipe.When the second startup device sets the time after can persistently preparing the methanol of gasification, it is possible to close above-mentioned device for rapidly starting, thus reducing the dependence to extra powers such as electric energy further.

In addition, described device for producing hydrogen 20 includes heat exchanger, vaporizer, reformer chamber；Membrane separation device is arranged in separation chamber, and separation chamber is arranged at the top of reformer chamber.Described liquid container is connected with device for producing hydrogen；Liquid container stores the first alcohol and water of liquid.

First alcohol and water in described liquid container is delivered to heat exchanger heat exchange by raw material conveying device, enters vaporizer gasification after heat exchange；Methanol vapor and steam after gasification enter reformer chamber, and it is 300 DEG C～420 DEG C that reformer chamber is provided with catalyst, reformer chamber bottom and middle portion temperature.The temperature on described reformer chamber top is 400 DEG C～570 DEG C；Reformer chamber is connected by connecting line with separation chamber, all or part of top being arranged at reformer chamber of connecting line, and the high temperature that can pass through reformer chamber top continues the heating gas from reformer chamber output；Described connecting line is as the buffering between reformer chamber and separation chamber so that identical or close with the temperature of separation chamber from the temperature of the gas of reformer chamber output.Temperature in described separation chamber is set as 350 DEG C～570 DEG C；It is provided with membrane separator in separation chamber, obtains hydrogen from the aerogenesis end of membrane separator.By above-mentioned improvement, it is possible to ensure the low temperature requirements of reformer chamber catalyst and the high temperature requirement of separation chamber respectively, and then improve hydrogen preparation efficiency；Meanwhile, the preheating method (separation chamber is arranged at the top of reformer chamber) of the present invention is very convenient.

Additionally, described raw material conveying device provides power, by the feedstock transportation in liquid container to device for producing hydrogen；Described raw material conveying device provides the pressure of 0.15～5MPa to raw material so that the hydrogen that device for producing hydrogen prepares has enough pressure.The hydrogen that described device for producing hydrogen prepares is delivered to membrane separation device and is easily separated, for the difference of inside and outside pressure of membrane separation device of separating hydrogen gas be more than or equal to 0.7MPa.By this improvement so that the hydrogen that device for producing hydrogen prepares has enough pressure, can improve hydrogen production efficiency and the purity of prepared hydrogen.

After described hydrogen producer starts, hydrogen producer is provided by the hydrogen that device for producing hydrogen prepares and runs the required energy；At this point it is possible to closedown device for rapidly starting.The hydrogen partial prepared due to device for producing hydrogen is or/and residual air maintains hydrogen producer operation by burning, such that it is able to reduce the dependence to extra power, adaptive ability is strong.

Additionally, refer to Fig. 5, Fig. 6, described hydrogen delivery tube road 60 is provided with spring safety valve 61, and spring safety valve 61 includes valve body, spring mechanism, end of upspringing；Described raw material conveying device 50 includes delivery pump, and end of upspringing arranges (certain raw material conveying device 50 can also be other power set) near the switch of delivery pump, can disconnect the switch of raw material conveying device when end of upspringing is upspring.By arranging mechanical safety valve on hydrogen delivery tube road, when air pressure reaches setting value, mechanical safety valve is opened, and can control raw material conveying device stopping transferring raw material.Such that it is able to improve the safety that equipment runs, it is prevented that hydrogen leak and blast.

Specifically, in the present embodiment, the switch of described delivery pump includes contact-segment 62 and three ports, three port respectively first port the 63, second port the 64, the 3rd ports 65.One end of described contact-segment 62 is rotationally arranged at the first port 63, and the first port 63 connects delivery pump；The other end of contact-segment 62 can contact the second port 64 or the 3rd port 65.

Described second port 64 connects power supply, when the first port 63 connects the second port 64, can control delivery pump work.Described 3rd port 65 connects alarm transmitting device, when the first port connects three ports 65, energy controls conveying air pump inoperative, and alarm transmitting device sends the extremely corresponding server of warning message (as by the mode of note) or client simultaneously, it is possible to notify corresponding personnel.

Described hydrogen gas generation device connects hydrogen producer, and the Partial DC electricity sent is delivered to hydrogen producer；Hydrogen producer drives electromagnetic heater to be reformer chamber, separation chamber's heating by the unidirectional current oneself prepared；Meanwhile, also the unidirectional current sent is delivered to the deep sea water extracting device of system, sea water purifying plant, oxygen delivery devices, water generation equipment, runs for these equipment, go back hydrogen supply gas electric generating apparatus self-operating simultaneously.

Described hydrogen producer includes electromagnetic heater；Electromagnetic heater includes forming the reformation cylinder body of reformer chamber, forming the separation cylinder body of separation chamber, it is arranged at the first heating coil outside reformation cylinder body, the second heating coil that splitter cylinder is external, the temperature sensor in reformation cylinder body, splitter cylinder body, pressure transducer, and electromagnetic controller；Electromagnetic controller heats the electric current of coil, the second heating coil according to the Data Control first that temperature sensor, pressure transducer sense, reformer chamber, separation chamber can be made moment to reach design temperature.

Described hydrogen producer also includes electric energy estimation block, hydrogen prepares detection module, electric energy memory module；The electric energy that when whether the electric energy that described electric energy estimation block sends in real time in order to estimate hydrogen gas generation device can meet reformation, separation, needs consume；If it is satisfied, then closedown device for rapidly starting.

Whether hydrogen prepares the hydrogen that detection module prepared in real time for detecting hydrogen producer stable；If hydrogen prepared by hydrogen producer is unstable, then controls device for rapidly starting and be again started up, and the electric energy obtained is partially stored in electric energy memory module, use when electric energy is not enough to the consumption providing hydrogen producer.

Referring to Fig. 7, in the present embodiment, described hydrogen gas generation device 200 is fuel cell system, and fuel cell system includes: gas supply device, pile 201；Described gas supply device utilizes the gas of compression as power, and automatic transport is to pile 201.

In the present embodiment, gas supply device is compressed gas body feeding 202, and described compression gas enters pile 201 after being delivered to a mixing container 203, one end of mixing container 203 connects air；Natural air is reacted by the power that compression gas produces after entering mixing container 203 in setting ratio inspiration pile, regulates oxygen content.

Described fuel cell system also includes air intake conduit, outlet pipe, and air intake conduit, outlet pipe are all through humidification system 204.The gas of described compression is mainly oxygen (can also be air)；Natural air enters pile 201 with compressed oxygen after mixing container mixing.

Described fuel cell system also includes gas regulating system, and gas regulating system is arranged in mixing container 203；Described gas regulating system includes valve regulated and controls device, and oxygen content sensor is or/and compress gas compression ratio sensor.

Described oxygen content sensor is in order to sense the air of mixing and the content of oxygen in oxygen in mixing container, and the data sensed is sent to valve regulated control device.

Described compression gas compression ratio sensor is in order to sense the compression ratio of compressed oxygen, and the data sensed is sent to valve regulated control device.

Described valve regulated controls device according to oxygen content sensor or/and the sensing result of compression gas compression ratio sensor regulates oxygen delivery valve door, air entrainment valve door, controls the conveying ratio (if natural air ratio can be 0-70%) of compressed oxygen, natural air；Mixing gas is pushed to pile reaction by the power that compressed oxygen produces after entering mixing container, utilizes natural air to do dilution decompression.

Described humidification system 204 includes humidity exchanging container, humidity exchange pipeline, and humidity exchange pipeline is a part for air intake conduit；After reaction, gas is delivered to humidity exchanging container by outlet pipe.

The material of described humidity exchange pipeline is only permeable airtight so that after reaction, gas and natural air carry out humidity exchange, and cannot circulate between gas.Humidity exchange pipeline spiral in humidity exchanging container is arranged, it is possible to sufficiently conducted humidity exchanges.

Referring to Fig. 9, described methanol Preparation equipment includes: nitrogen gas conveying device A1, hydrogen conveyor A2, carbon dioxide conveyer device A3, the first blender A4, the second gaseous mixture A5, micro fixed-bed reactor A7, counterbalance valve A8, alcohol-water separation device A6, chromatograph A9, methanol solution gasifying device, methanol collect container, main control module.

Described nitrogen gas conveying device A1 includes nitrogen storage container, the first transfer pipeline, and the first transfer pipeline is provided with the first stop valve A11, the first mass flowmenter A12.

Described carbon dioxide conveyer device A3 includes carbon dioxide storage container, the second transfer pipeline, and the second transfer pipeline is provided with the second stop valve, the second mass flowmenter.

Described hydrogen conveyor A3 includes hydrogen storage vessel, the 3rd transfer pipeline, the 4th transfer pipeline, and the 3rd transfer pipeline is provided with the 3rd stop valve, the 3rd mass flowmenter, and the 4th transfer pipeline is provided with the 4th stop valve, the 4th mass flowmenter.

Described hydrogen storage vessel A3 is connected by the 3rd transfer pipeline and the first transfer pipeline, and the 3rd transfer pipeline and the first transfer pipeline are intersected in one first three-way valve A13.

Described hydrogen storage vessel is connected by the 4th transfer pipeline and the second transfer pipeline, and the 4th transfer pipeline and the second transfer pipeline are intersected in one first cross valve A14.

Described first three-way valve A13 and the first blender A4 connects, and the other end of the first blender A4 and the second three-way valve A15 connect；Second three-way valve A15 connects micro fixed-bed reactor A7 by the 5th transfer pipeline, and the 5th transfer pipeline is provided with the 5th mass flowmenter, pressure gage.

The other end of described micro fixed-bed reactor A7 connects the 4th three-way valve A16, the 4th three-way valve A16 and is also connected with the other end connection one second cross valve A10 of counterbalance valve A8, counterbalance valve A8.

Described first cross valve A14 and the second blender A5 connects, and the other end of the second blender A5 and the 3rd three-way valve A17 connect；Alcohol-water separation device A6, the second three-way valve A15 connect the 3rd three-way valve A17, and alcohol-water separation device A6, methanol solution gasifying device, chromatograph A9 connect the second cross valve A10；Methanol solution gasifying device is collected container with methanol and is connected.

Described methanol Preparation equipment also includes generating electricity by natural energy device, utilizes solar energy or/and wind energy is or/and bioenergy power generation, utilizes the electric energy sent that water is hydrolyzed to hydrogen and oxygen, is methanol by the hydrogen collected and carbon dioxide preparation.The energy that methanol Preparation equipment uses can be the electric energy utilizing the natural energy resources such as solar energy, wind energy to be transformed.

Embodiment two

The present embodiment and embodiment one are distinctive in that, in the present embodiment, described water hydrogen electricity generation system also includes air pressure adjustment subsystem, Collection utilization subsystem.

Described air pressure adjustment subsystem includes microprocessor, gas pressure sensor, valve positioner, air outlet valve, outlet pipe；Described gas pressure sensor is arranged in transfer conduit, in order to sense the barometric information in transfer conduit, and sends the barometric information of sensing to microprocessor；This barometric information received from gas pressure sensor is compared by described microprocessor with setting threshold interval；When the pressure data received is higher than the maximum setting threshold interval, microprocessor controls valve positioner and opens the air outlet valve setting time, air pressure in transfer conduit is made to be in set point, one end of outlet pipe connects air outlet valve simultaneously, the other end connects described hydrogen manufacturing subsystem, is that the firing equipment that needs of hydrogen manufacturing subsystem is heated by burning；When the pressure data received is lower than the minima setting threshold interval, microprocessor controls described hydrogen manufacturing subsystem and accelerates the transporting velocity of raw material.

Described Collection utilization subsystem connects the Vent passageway of hydrogen gas generating system, hydrogen, oxygen gas and water is collected respectively from expellant gas, utilize the hydrogen collected, oxygen for hydrogen manufacturing subsystem or/and hydrogen gas generating system, the water collected is as the raw material of hydrogen manufacturing subsystem, thus recycling.Described Collection utilization subsystem includes hydrogen/oxygen separator, hydrogen water separator, hydrogen check-valves, oxygen water separator, oxygen check valve, by hydrogen and oxygen separation, is then separated from water by hydrogen respectively, oxygen is separated from water.

In sum, the carbon dioxide recycle formula water hydrogen electricity generation system that the present invention proposes, the methanol needed for electricity generation system can be made by oneself, and avoid the discharge of carbon dioxide.Device for producing hydrogen volume of the present invention is little, utilizes distinctive catalyst formulation and palladium film to purify, and the hydrogen of preparation is quickly, stable, purity is high, it is possible to provide stable input energy sources for automobile.The methanol Preparation equipment of the present invention can improve preparation efficiency, improves the concentration preparing methanol.

Here description of the invention and application is illustrative, is not wishing to limit the scope of the invention in above-described embodiment.The deformation of embodiments disclosed herein and change are possible, for those skilled in the art embodiment replace and the various parts of equivalence are known.It should be appreciated by the person skilled in the art that when without departing from the spirit of the present invention or substitutive characteristics, the present invention can in other forms, structure, layout, ratio, and realize with other assembly, material and parts.When without departing from the scope of the invention and spirit, it is possible to embodiments disclosed herein is carried out other deformation and changes.

Claims

1. a carbon dioxide recycle formula water hydrogen electricity generation system, it is characterized in that, described carbon dioxide recycle formula water hydrogen electricity generation system includes: hydrogen production by methanol system, hydrogen gas generating system, methanol Preparation equipment, hydrogen production by methanol system is connected with hydrogen gas generating system, and hydrogen gas generating system is connected with methanol Preparation equipment；The electric energy work that methanol Preparation equipment is sent by hydrogen gas generating system；

Described fuel cell system also includes humidification system, and humidification system includes humidity exchanging container, humidity exchange pipeline, and humidity exchange pipeline is a part for air intake conduit；After reaction, gas is delivered to humidity exchanging container by outlet pipe；

The material of described humidity exchange pipeline is only permeable airtight so that after reaction, gas and natural air carry out humidity exchange, and cannot circulate between gas；

2. a carbon dioxide recycle formula water hydrogen electricity generation system, it is characterized in that, described carbon dioxide recycle formula water hydrogen electricity generation system includes: hydrogen production by methanol system, hydrogen gas generating system, methanol Preparation equipment, hydrogen production by methanol system is connected with hydrogen gas generating system, and hydrogen gas generating system is connected with methanol Preparation equipment；

3. carbon dioxide recycle formula water hydrogen electricity generation system according to claim 2, it is characterised in that:

Described hydrogen production by methanol system includes storing container；The middle part storing container is provided with dividing plate, and the side of dividing plate arranges reaction liquid, and opposite side arranges the carbon dioxide of hydrogen gas generating system release, the liquid then compressed or solid-state；Dividing plate is connected to pushing mechanism, and when the liquid stored in container reduces or carbon dioxide increases up to impose a condition, pushing mechanism drives dividing plate action, reduces the volume of storage reaction liquid regions, increases the volume in storage carbon dioxide region.

4. carbon dioxide recycle formula water hydrogen electricity generation system according to claim 3, it is characterised in that:

Described storage container also includes controlling module, induction module；Described driving mechanism includes motor, and induction module includes pressure transducer or/and liquid level sensor；Described induction module, in order to sense the amount of reaction liquid in container, senses the amount of the carbon dioxide of hydrogen gas generating system release, the liquid then compressed or solid-state simultaneously；And sensed data is sent to controlling module；The Data Control driving mechanism that described control module senses according to the induction module action to space mechanism；When liquid in liquid storage container reduces or carbon dioxide increases up to impose a condition, driving mechanism drives space mechanism action, reduces the volume of reaction liquid, increases the volume of carbon dioxide；Described storage device also includes liquefying plant or/and solidification equipment, by the co 2 liquefaction collected or/and solidify.

5. carbon dioxide recycle formula water hydrogen electricity generation system according to claim 2, it is characterised in that:

Described Collection utilization subsystem includes hydrogen/oxygen separator, hydrogen water separator, hydrogen check-valves, oxygen water separator, oxygen check valve, by hydrogen and oxygen separation, is then separated from water by hydrogen respectively, oxygen is separated from water.

6. carbon dioxide recycle formula water hydrogen electricity generation system according to claim 5, it is characterised in that:

7. carbon dioxide recycle formula water hydrogen electricity generation system according to claim 5, it is characterised in that:

The initial start energy of described device for rapidly starting is that some solar energys start module, and solar energy starts solar panel that module includes being sequentially connected with, solar energy-electric energy change-over circuit, solaode；Solar energy starts module provides electric energy for the first heating arrangements；Or, the initial start energy of described device for rapidly starting is manual generator, and the electric energy sent is stored in battery by manual generator.

8. carbon dioxide recycle formula water hydrogen electricity generation system according to claim 5, it is characterised in that:

9. carbon dioxide recycle formula water hydrogen electricity generation system according to claim 2, it is characterised in that: