CN103618100A - Instant hydrogen-production power generation system and method - Google Patents
Instant hydrogen-production power generation system and method Download PDFInfo
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- CN103618100A CN103618100A CN201310578035.9A CN201310578035A CN103618100A CN 103618100 A CN103618100 A CN 103618100A CN 201310578035 A CN201310578035 A CN 201310578035A CN 103618100 A CN103618100 A CN 103618100A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
- H01M8/04104—Regulation of differential pressures
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- H—ELECTRICITY
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- H01M8/00—Fuel cells; Manufacture thereof
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Abstract
The invention discloses an instant hydrogen-production power generation system and method. The system comprises a hydrogen-production subsystem, a power generation subsystem and a collection and utilization subsystem, wherein the hydrogen-production subsystem, power generation subsystem and collection and utilization subsystem are connected sequentially; the hydrogen-production subsystem uses methanol water to produce hydrogen, and transfers the produced hydrogen to the power generation subsystem in time through a transfer pipeline for power generation; and the collection and utilization subsystem is connected with an exhaust channel outlet of the power generation subsystem, and is used for collecting water from discharged gas or collecting water as the raw material of the hydrogen-production subsystem. The system and method can collect residual gas discharged from the power generation subsystem, and extract hydrogen, oxygen and water from the residual gas; and the hydrogen and oxygen can be combusted to release heat so as to provide heat energy for the power generation subsystem, and the water can be transferred to the hydrogen-production subsystem for cyclic utilization, so that the system does not need any additional water source. The system and method can enhance the power generation efficiency of the system and save the energy source.
Description
Technical field
The invention belongs to hydrogen preparation and applied technical field, relate to a kind of hydrogen gas generating system, relate in particular to a kind of instant hydrogen manufacturing electricity generation system; Meanwhile, the present invention also discloses a kind of instant hydrogen manufacturing electricity-generating method.
Background technology
In numerous new forms of energy, Hydrogen Energy will become the optimal energy of 21 century.This is because in the situation that coal, gasoline and the hydrogen of burning identical weight, the energy that hydrogen produces is maximum, and the product of its burning is water, there is no lime-ash and waste gas, does not pollute the environment; And coal and oil combustion generate, be carbon dioxide and sulfur dioxide, can produce respectively greenhouse effect and acid rain.Coal and reserves are limited, and hydrogen is mainly stored in water, and after burning, unique product is also water, can produce continuously hydrogen, is finished never.
Hydrogen is a kind of colourless gas.The 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 light especially, and it is all gently more than gasoline, natural gas, kerosene, thereby 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 can be up to 2500 ℃, thereby the conventional hydrogen cutting of people or weldable steel iron material.
In the Nature, the distribution of hydrogen is very extensive.Water is exactly large " warehouse " of hydrogen, wherein contains 11% hydrogen.There is 1.5% hydrogen earth Rio; All contain hydrogen in oil, coal, natural gas, animal and plant body etc.The main body of hydrogen is that the form with compound water exists, and earth surface approximately 70% is covered by water, and moisture storage capacity is very large, therefore can say, hydrogen is the energy of " inexhaustible, nexhaustible ".If can be with suitable method preparing hydrogen from water, hydrogen also will be the energy that a kind of price is quite cheap so.
Having many uses of hydrogen, applicability 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.For example, hydrogen storage metal has the ability of inhaling hydrogen heat release and absorbing heat and putting hydrogen, heat can be stored, and as heating and air-conditioning in room, uses.
Hydrogen, as gaseous fuel, is first used on automobile.In May, 1976, the U.S. develops a kind of automobile of making fuel with hydrogen; Afterwards, Japan also succeeded in developing a kind of automobile that liquified hydrogen is fuel of take; In the latter stage seventies, the Mercedes of front Germany tests hydrogen, and they have only used five kg of hydrogen, has just made running car 110 kilometers.
As motor vehicle fuel, not only clean with hydrogen, easily start at low temperatures, and little to the corrosiveness of engine, can extend the useful life of engine.Because hydrogen can evenly mix with air, can save vaporizer used on general automobile completely, thereby can simplify the structure of existing automobile.More interestingly, need only the hydrogen that adds 4% in gasoline.Use it as automobile engine fuel, just can fuel-economizing 40%, and without petrol engine being done to great improvement.
Hydrogen is easy to become liquid at certain pressure and temperature, thereby it is all very convenient by iron flask car, on-highway tractor or ship transportation.Liquid hydrogen both can be used as the fuel of automobile, aircraft, also can be used as the fuel of rocket, guided missile.The fly to Apollo Personnel investigation Program of the moon of the U.S. " Long March carrier rocket that number spaceship and China launch a man-made satellite., all with liquified hydrogen, make fuel.
In addition, use hydrogen-hydrogen fuel cell Hydrogen Energy directly can also be changed into electric energy, make utilizing of Hydrogen Energy more convenient.At present, this fuel cell is used on spaceship and submarine, and effect is pretty good.Certainly, because cost is higher, be also difficult to generally use for the moment.
The annual production of hydrogen is about 3,600 ten thousand tons in the world now, and wherein the overwhelming majority is produced from oil, coal and natural gas, and this must consume original just fossil fuel very in short supply; Separately having 4% hydrogen is to produce by the method for brine electrolysis, but the electric energy consuming is too many, very calculates, and therefore, people are trying to explore to study hydrogen manufacturing new method.And can reduce the energy consumption in Chemical Manufacture and reduce costs with methyl alcohol, water reformation hydrogen production, be expected to substitute the technique of " water electrolysis hydrogen production " be called as electricity-eating tiger, utilize advanced methanol vapor to reform--pressure swing adsorption making pure hydrogen and be rich in CO
2mist, through further reprocessing, can obtain hydrogen and carbon dioxide gas simultaneously.
Methyl alcohol and steam pass through catalyst under certain temperature, pressure condition, under the effect of catalyst, the transformationreation of methanol decomposition reaction and carbon monoxide occurs, generate hydrogen and carbon dioxide, this is the gas solid catalytic reaction system of component more than, many reactions.Reactional equation is as follows:
CH
3OH→CO+2H
2 (1)
H
2O+CO→CO
2+H
2 (2)
CH
3OH+H
2O→CO
2+3H
2 (3)
The H that reforming reaction generates
2and CO
2, then pass through the separation of palladium film by H
2and CO
2separation, obtains high-purity hydrogen.The power consumption of pressure swing adsorption method is high, equipment is large, and is not suitable for small-scale hydrogen preparation.
In the preparation of existing hydrogen and electricity generation system, hydrogen gas generation chance is discharged some residual air, mainly comprises the hydrogen, oxygen, steam of not yet fully reaction etc., is nowadays that these gases are discharged, and hydrogen is wherein hazardous gas, has certain potential safety hazard.Meanwhile, these gases have certain value.
In addition, existing hydrogen gas generating system, normally utilizes the hydrogen gas generation having prepared, and preparing hydrogen is separated with hydrogen gas generation.First utilize hydrogen producer to prepare hydrogen, hydrogen is positioned in hydrogen gas buffer, then by the hydrogen gas generation in hydrogen gas buffer.The volume of hydrogen gas buffer is comparatively huge, Portable belt not, and mobility is poor, thereby has restricted the portability of hydrogen preparation and generating equipment.
In view of this, nowadays in the urgent need to designing a kind of new hydrogen gas generating system, to overcome the above-mentioned defect of existing hydrogen gas generating system.
Summary of the invention
Technical problem to be solved by this invention is: a kind of instant hydrogen manufacturing electricity generation system is provided, can effectively utilizes the residual air after power generation sub-system, improve the efficiency of system.
In addition, the present invention also provides a kind of instant hydrogen manufacturing electricity-generating method, can effectively utilize the residual air after power generation sub-system, improves the efficiency of system.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
An instant hydrogen manufacturing electricity generation system, described system comprises: hydrogen manufacturing subsystem, air pressure adjustment subsystem, power generation sub-system, collection utilize subsystem, hydrogen manufacturing subsystem, air pressure adjustment subsystem, power generation sub-system, collection utilize subsystem to connect successively;
Described hydrogen manufacturing subsystem utilizes methanol-water to prepare hydrogen, and described hydrogen manufacturing subsystem comprises solid hydrogen reservoir vessel, liquid container, raw material conveying device, hydrogen producer, membrane separation device;
Described hydrogen producer comprises heat exchanger, vaporizer, reformer chamber; Membrane separation device is arranged at the inside that Nei， separation chamber, separation chamber is arranged at reformer chamber;
Described solid hydrogen reservoir vessel, liquid container are connected with hydrogen producer respectively; In liquid container, store liquid first alcohol and water;
In described solid hydrogen reservoir vessel, store solid hydrogen, when hydrogen generating system starts, by gasification module, solid hydrogen is converted to gaseous hydrogen, gaseous hydrogen is by burning heat release, for hydrogen producer provides startup heat energy, as the startup energy of hydrogen producer;
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 reformer chamber is provided with catalyst, and reformer chamber bottom and middle part temperature are 300 ℃～420 ℃;
The temperature on described reformer chamber top is 400 ℃～570 ℃; Reformer chamber is connected by connecting line with separation chamber, and heating can be continued from the gas of reformer chamber output in all or part of top that is arranged at reformer chamber of connecting line by the high temperature on reformer chamber top; Described connecting line, as the buffering between reformer chamber and separation chamber, makes from the temperature of gas of reformer chamber output identical with the temperature of separation chamber or approaching;
Temperature Setting in described separation chamber is 350 ℃～570 ℃; In separation chamber, be provided with membrane separator, from the aerogenesis end of membrane separator, obtain hydrogen;
Described raw material conveying device provides power, and the raw material in liquid container is delivered to hydrogen producer; Described raw material conveying device provides the pressure of 0.15～5MPa to raw material, make the hydrogen that hydrogen producer makes have enough pressure;
Described hydrogen producer starts after hydrogen manufacturing, and the hydrogen partial that hydrogen producer makes is or/and residual air maintains hydrogen producer by burning moves;
The hydrogen that described hydrogen producer makes is delivered to membrane separation device and carries out separation, for separating of the difference of the inside and outside pressure of the membrane separation device of hydrogen, is more than or equal to 0.7M Pa;
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 passes through transfer conduit real-time Transmission to power generation sub-system by the hydrogen making; Described transfer conduit is provided with air pressure adjustment subsystem, for adjusting the air pressure of transfer conduit; The hydrogen gas generation that described power generation sub-system utilizes hydrogen manufacturing subsystem to make;
Described air pressure adjustment subsystem comprises microprocessor, gas pressure sensor, valve positioner, air outlet valve, outlet pipe; Described gas pressure sensor is arranged in transfer conduit, in order to respond to the barometric information in transfer conduit, and the barometric information of induction is sent to microprocessor; Described microprocessor is compared this barometric information receiving from gas pressure sensor and setting threshold interval; When the maximum of the pressure data receiving higher than setting threshold interval, microprocessor by-pass valve control controller opens air outlet valve setting-up time, make in transfer conduit air pressure in setting range, one end of outlet pipe connects air outlet valve simultaneously, the other end connects described hydrogen manufacturing subsystem, and the firing equipment that needs that is hydrogen manufacturing subsystem by burning heats; When the minimum value of the pressure data receiving lower than setting threshold interval, microprocessor is controlled the transporting velocity that described hydrogen manufacturing subsystem is accelerated raw material;
Described collection utilizes subsystem to connect the exhaust passage outlet of power generation sub-system, from the gas of discharging, collects water, utilizes the water collected as the raw material of hydrogen manufacturing subsystem, thereby recycles;
Described collection utilizes subsystem to comprise hydrogen separator, hydrogen check-valves, oxygen separator, oxygen check valve, hydrogen is separated with water, oxygen is separated with water.
An instant hydrogen manufacturing electricity generation system, described system comprises: hydrogen manufacturing subsystem, power generation sub-system, collection utilize subsystem, hydrogen manufacturing subsystem, power generation sub-system, collection utilize subsystem to connect successively;
Described hydrogen manufacturing subsystem utilizes methanol-water to prepare hydrogen, by the hydrogen making by transfer conduit real-time Transmission to power generation sub-system for generating;
Described collection utilizes subsystem to connect the exhaust passage outlet of power generation sub-system, collects water, maybe by the raw material of the water hydrogen manufacturing subsystem of collecting from the gas of discharging.
As a preferred embodiment of the present invention, described collection utilizes subsystem to comprise air-water separator, the water of collecting is delivered to hydrogen manufacturing subsystem, thereby recycles.
As a preferred embodiment of the present invention, described collection utilizes subsystem to comprise hydrogen separator, hydrogen check-valves, and the exhaust passage outlet of power generation sub-system connects the entrance of hydrogen separator, in the pipeline that hydrogen separator exit connects, is provided with hydrogen check-valves; Described hydrogen separator is for separating of hydrogen and water.
As a preferred embodiment of the present invention, described collection utilizes subsystem also to comprise hydrogen/oxygen separator, for separating of hydrogen and oxygen; Hydrogen/oxygen separator is arranged between the outlet of described power generation sub-system exhaust passage and hydrogen separator.
As a preferred embodiment of the present invention, described collection utilizes subsystem also to comprise oxygen separator, oxygen check valve, for collecting oxygen;
Described collection utilize hydrogen that subsystem collects and oxygen for hydrogen manufacturing subsystem or/and power generation sub-system.
A preparing hydrogen, generating power method for said system, described preparing hydrogen, generating power method comprises the steps:
Described hydrogen manufacturing subsystem utilizes methanol-water to prepare hydrogen, and the hydrogen making is passed through to transfer conduit real-time Transmission to power generation sub-system;
The hydrogen gas generation that described power generation sub-system utilizes hydrogen manufacturing subsystem to make;
Described collection utilizes subsystem to connect the exhaust passage outlet of power generation sub-system, collects water, maybe by the raw material of the water hydrogen manufacturing subsystem of collecting from the gas of discharging.
As a preferred embodiment of the present invention, described method also comprises: oxygen is collected and utilized step, by collection, utilizes subsystem to collect oxygen; By the hydrogen of collecting and oxygen for hydrogen manufacturing subsystem or/and power generation sub-system.
As a preferred embodiment of the present invention, described method also comprises: described method also comprises: hydrogen is collected and utilized step, by collection, utilizes subsystem to collect hydrogen; By the hydrogen of collecting and oxygen for hydrogen manufacturing subsystem or/and power generation sub-system.
Beneficial effect of the present invention is: instant hydrogen manufacturing electricity generation system and method that the present invention proposes, can collect the residual air that power generation sub-system is discharged, and therefrom extract hydrogen, oxygen, water, the heat release of can burning of hydrogen, oxygen, for power generation sub-system provides heat energy, water can transfer to hydrogen manufacturing subsystem and recycle, and system does not need extra water source.The present invention can raising system the efficiency of generating, save the energy.
In addition, the present invention can also utilize the standby hydrogen gas generation of immediate system, without hydrogen gas buffer, by air pressure adjustment subsystem, adjusts the hydrogen gas pressure in transfer conduit; Because the volume of air pressure adjustment subsystem is very little, thereby can further improve portability, the mobility of preparing hydrogen, generating power system.
Accompanying drawing explanation
Fig. 1 is the composition schematic diagram of the instant hydrogen manufacturing electricity generation system of the present invention in embodiment mono-.
Fig. 2 collects the work schematic diagram that utilizes subsystem in embodiment mono-.
Fig. 3 is the composition schematic diagram of the instant hydrogen manufacturing electricity generation system of the present invention in embodiment bis-.
Fig. 4 is the composition schematic diagram of hydrogen manufacturing subsystem in embodiment tri-.
Fig. 5 is the composition schematic diagram of hydrogen manufacturing subsystem in embodiment tetra-.
Fig. 6 is the structural representation of the first starting drive in embodiment tetra-.
Embodiment
Below in conjunction with accompanying drawing, describe the preferred embodiments of the present invention in detail.
Embodiment mono-
Refer to Fig. 1, the present invention has disclosed a kind of instant hydrogen manufacturing electricity generation system, described system comprises: hydrogen manufacturing subsystem 100, power generation sub-system 300, collection utilize subsystem 400, and hydrogen manufacturing subsystem 100, power generation sub-system 200, collection utilize subsystem 400 to connect successively;
Described hydrogen manufacturing subsystem 100 utilizes methanol-water to prepare hydrogen, by the hydrogen making by transfer conduit real-time Transmission to power generation sub-system 300 for generating;
Described collection utilizes subsystem 400 to connect the exhaust passage outlet of power generation sub-system 300, from the gas of discharging, collects hydrogen, or utilize the hydrogen collected for hydrogen manufacturing subsystem 100 or/and power generation sub-system 300.
As shown in Figure 2, described collection utilizes subsystem 400 to comprise hydrogen separator 401, hydrogen check-valves 402, the exhaust passage outlet of power generation sub-system 300 connects the entrance of hydrogen separator 401, in the pipeline that hydrogen separator 401 exits connect, is provided with hydrogen check-valves 402, prevents that hydrogen from pouring in down a chimney; Described hydrogen separator 401 is for separating of hydrogen and water.In addition, described collection utilizes subsystem also to comprise hydrogen/oxygen separator, for separating of hydrogen and oxygen; Hydrogen/oxygen separator is arranged between the outlet of described power generation sub-system exhaust passage and hydrogen separator.
In the present embodiment, described collection utilizes subsystem 400 also to comprise oxygen separator 411, oxygen check valve 412, for collecting oxygen.Described collection utilize hydrogen that subsystem 400 collects with oxygen for hydrogen manufacturing subsystem 100, also can be for power generation sub-system 300 uses.In addition, the oxygen of collecting can be deposited in and set in container, for people's oxygen uptake; The water of collecting can be drunk for people.
Because utilizing subsystem, described collection comprises air-water separator (as above-mentioned hydrogen separator, oxygen separator), therefore can collect water (than the many several times also of the moisture in raw material, because also contain hydrogen atom in methyl alcohol, after making hydrogen, obtain water with oxygen reaction), water is delivered to hydrogen manufacturing subsystem 100, raw water can recycle, without other interpolation.
Therefore, system of the present invention can be collected the utilities such as hydrogen, oxygen, water from the residual air of power generation sub-system, can improve the generating efficiency of system, simultaneously conservation (water).
Embodiment bis-
The difference of the present embodiment and embodiment mono-is, in the present embodiment, refer to Fig. 3, the instant hydrogen manufacturing electricity generation system of the present invention comprises hydrogen manufacturing subsystem 100, air pressure adjustment subsystem 200, power generation sub-system 300, and hydrogen manufacturing subsystem 100, air pressure adjustment subsystem 200, power generation sub-system 300 connect successively.Described hydrogen manufacturing subsystem 100 utilizes methanol-water to prepare hydrogen, and the hydrogen making is passed through to transfer conduit real-time Transmission to power generation sub-system 300; Described transfer conduit is provided with air pressure adjustment subsystem 200, for adjusting the air pressure of transfer conduit; The hydrogen gas generation that described power generation sub-system 300 utilizes hydrogen manufacturing subsystem to make.
Described hydrogen manufacturing subsystem utilizes methanol-water to prepare hydrogen, and described hydrogen manufacturing subsystem comprises solid hydrogen reservoir vessel, liquid container, raw material conveying device, hydrogen producer, membrane separation device.
As shown in Figure 3, described air pressure adjustment subsystem 200 comprises microprocessor 21, gas pressure sensor 22, valve positioner 23, air outlet valve 24, outlet pipe 25.Described gas pressure sensor 22 is arranged in transfer conduit, in order to respond to the barometric information in transfer conduit, and the barometric information of induction is sent to microprocessor 21; Described microprocessor 21 is compared this barometric information and the setting threshold interval that from gas pressure sensor 22, receive, and controls the switch of air outlet valve 24 with this.When the maximum of the pressure data receiving higher than setting threshold interval, microprocessor 21 by-pass valve control controllers 23 are opened air outlet valve setting-up time, make in transfer conduit air pressure in setting range. preferably, one end of outlet pipe 25 connects air outlet valve 24, the other end connects described hydrogen manufacturing subsystem 100, and the firing equipment (as reformer chamber) that needs that is hydrogen manufacturing subsystem 100 by burning heats; When the minimum value of the pressure data receiving lower than setting threshold interval, microprocessor 21 is controlled described hydrogen manufacturing subsystem 100 and is accelerated the transporting velocity of raw material, thereby improves hydrogen manufacturing speed.
More than introduced the instant hydrogen manufacturing electricity generation system of the present invention, the present invention, when disclosing above-mentioned instant hydrogen manufacturing electricity generation system, also discloses a kind of electricity-generating method of above-mentioned instant hydrogen manufacturing electricity generation system, and described electricity-generating method comprises:
[step S1] described hydrogen manufacturing subsystem utilizes methanol-water to prepare hydrogen, and the hydrogen making is passed through to transfer conduit real-time Transmission to power generation sub-system.
The process that described hydrogen manufacturing subsystem is prepared hydrogen comprises:
In solid hydrogen reservoir vessel, store solid hydrogen, when hydrogen generating system starts, by gasification module, solid hydrogen is converted to gaseous hydrogen, gaseous hydrogen is by burning heat release, for hydrogen producer provides startup heat energy, as the startup energy of hydrogen producer;
Described raw material conveying device provides power, and the raw material in liquid container is delivered to hydrogen producer; Described raw material conveying device provides the pressure of 0.15～5M Pa to raw material, make the hydrogen that hydrogen producer makes have enough pressure;
Hydrogen producer is prepared hydrogen;
The hydrogen that described hydrogen producer makes is delivered to membrane separation device and carries out separation, for separating of the difference of the inside and outside pressure of the membrane separation device of hydrogen, is more than or equal to 0.7M Pa(as 1.1MPa).
[step S2] described transfer conduit is provided with air pressure adjustment subsystem, adjusts the air pressure in transfer conduit; Described gas pressure sensor is arranged in transfer conduit, the barometric information in induction transfer conduit, and the barometric information of induction is sent to microprocessor; Described microprocessor is controlled the switch of air outlet valve according to the barometric information of described gas pressure sensor induction.
Described air pressure adjustment subsystem specifically comprises while carrying out air pressure adjustment: described microprocessor is compared barometric information and the setting threshold interval of described gas pressure sensor induction; When the maximum of the pressure data receiving higher than setting threshold interval, microprocessor by-pass valve control controller opens air outlet valve setting-up time, makes in transfer conduit air pressure in setting range; When the minimum value of the pressure data receiving lower than setting threshold interval, microprocessor is controlled the transporting velocity that described hydrogen manufacturing subsystem is accelerated raw material.
The hydrogen gas generation that [step S3] described power generation sub-system utilizes hydrogen manufacturing subsystem to make.
Embodiment tri-
The difference of the present embodiment and embodiment mono-is, in the present embodiment, refer to Fig. 4, described hydrogen manufacturing subsystem utilizes methanol-water to prepare hydrogen, and described hydrogen manufacturing subsystem comprises solid hydrogen reservoir vessel 80, liquid container 10, raw material conveying device 50, hydrogen producer 20, membrane separation device 30.
Described solid hydrogen reservoir vessel 80, liquid container 10 are connected with hydrogen producer 20 respectively; In liquid container 10, store liquid first alcohol and water, in described solid hydrogen reservoir vessel 80, store solid hydrogen.
When hydrogen generating system starts, by gasification module, the solid hydrogen in solid hydrogen reservoir vessel 80 is converted to gaseous hydrogen, gaseous hydrogen is by burning heat release, for hydrogen producer 20 provides startup heat energy, as the startup energy of hydrogen producer 20.Certainly, solid hydrogen reservoir vessel 80 is not necessaries of the present invention, can start hydrogen producer 20 by other energy.
Described raw material conveying device 50 provides power, and the raw material in liquid container 10 is delivered to hydrogen producer 20; The pressure (as provide 0.2M Pa or 1.1M Pa or 1.2M Pa or 1.5M Pa or 5M Pa pressure) of 0.15～5M Pa is provided to raw material described raw material conveying device 50, and the hydrogen that hydrogen producer 20 is made has enough pressure.Described hydrogen producer 20 starts after hydrogen manufacturing, and the hydrogen partial that hydrogen producer 20 makes is or/and residual air maintains hydrogen producer 20 operations (certainly, the operation of hydrogen producer 20 can also be passed through other energy) by burning.
The hydrogen that described hydrogen producer 20 makes is delivered to membrane separation device 30 and carries out separation, for separating of the difference of the inside and outside pressure of the membrane separation device 30 of hydrogen be more than or equal to 0.7M Pa(as the inside and outside pressure of membrane separation device 30 be 0.7M Pa or 1.1M Pa or 1.2M Pa or 1.5M Pa or 5M Pa).
In the present embodiment, described membrane separation device 30 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%.The preparation technology of described membrane separation device 30 comprises the steps:
Step 1, porous ceramic is arranged in the vacuum chamber of magnetic control sputtering device;
Step 2, utilize the magnetic field of magnetic control sputtering device to produce mechanism to produce magnetic field, make metallic target produce deviation electric current, metallic target is as negative pole, thereby makes porous ceramic surface with magnetosphere body; The material of described metallic target is sputter precious metal, and described precious metal is palladium-silver, and mass percent palladium accounts for 75%～78%, and silver accounts for 22%～25%;
Step 3, when metallic target produces deviation electric current, the vacuum chamber of magnetic control sputtering device is heated, temperature is controlled at 350 ℃～800 ℃;
Gas in step 4, extraction vacuum chamber, the vacuum degree indoor when vacuum is less than 10
-2during Pa, in vacuum chamber, be filled with the argon gas of setting concentration;
Step 5, to metallic target, pass into electric current, carry out sputter coating; The ion that metallic target produces accelerates to fly in the process of porous ceramic surface and bumps with ar atmo under the effect of electric field, ionizes out a large amount of argon ions and electronics, and electronics flies to porous ceramic surface; Argon ion accelerates bombardment metallic target under the effect of electric field, sputters a large amount of metallic target target atom or molecule, is neutral target atom or molecule deposition on porous ceramic surface, forms the precious metal film of 1～15 μ m;
Wherein, in the process of sputter coating, also comprise argon concentration detecting step; Detect the argon concentration in vacuum chamber in real time or with setting-up time interval, when argon concentration, automatically open argon gas charging valve during lower than setting threshold, in vacuum chamber, be filled with argon gas, until the argon concentration in vacuum chamber meets setting threshold scope;
In the process of sputter coating, also comprise air pressure detecting step; Detect the air pressure in vacuum chamber in real time or with setting-up time interval, not interval at setting threshold when the air pressure that vacuum is indoor, the air pressure of adjusting in vacuum chamber is interval to setting threshold;
Step 6, in vacuum chamber, pass into atmosphere, take out workpiece.
Preferably, described hydrogen producer comprises heat exchanger, vaporizer, reformer chamber; Membrane separation device is arranged at the top that Nei， separation chamber, separation chamber is arranged at reformer chamber.
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 reformer chamber is provided with catalyst, and reformer chamber bottom and middle part temperature are 350 ℃～409 ℃; The temperature on described reformer chamber top is 400 ℃～570 ℃; Reformer chamber is connected by connecting line with separation chamber, and heating can be continued from the gas of reformer chamber output in all or part of top that is arranged at reformer chamber of connecting line by the high temperature on reformer chamber top; Described connecting line, as the buffering between reformer chamber and separation chamber, makes from the temperature of gas of reformer chamber output identical with the temperature of separation chamber or approaching; Temperature Setting in described separation chamber is 400 ℃～570 ℃; In separation chamber, be provided with membrane separator, from the aerogenesis end of membrane separator, obtain hydrogen.
More than introduced the composition of methanol-water hydrogen manufacturing subsystem, the present invention also discloses a kind of hydrogen production process that utilizes above-mentioned methanol-water hydrogen manufacturing subsystem, and described hydrogen production process comprises:
In [step 0] described solid hydrogen reservoir vessel, store solid hydrogen, when hydrogen generating system starts, by gasification module, solid hydrogen is converted to gaseous hydrogen, gaseous hydrogen is by burning heat release, for hydrogen producer provides startup heat energy, as the startup energy of hydrogen producer;
[step 1] described raw material conveying device provides power, and the raw material in liquid container is delivered to hydrogen producer; Described raw material conveying device provides the pressure of 0.15～5M Pa to raw material, make the hydrogen that hydrogen producer makes have enough pressure;
[step 2] hydrogen producer is prepared hydrogen; Specifically comprise:
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 reformer chamber is provided with catalyst, and reformer chamber bottom and middle part temperature are 300 ℃～420 ℃;
The temperature on described reformer chamber top is 400 ℃～570 ℃; Reformer chamber is connected by connecting line with separation chamber, and heating can be continued from the gas of reformer chamber output in all or part of top that is arranged at reformer chamber of connecting line by the high temperature on reformer chamber top; Described connecting line, as the buffering between reformer chamber and separation chamber, makes from the temperature of gas of reformer chamber output identical with the temperature of separation chamber or approaching;
Temperature Setting in described separation chamber is 350 ℃～570 ℃; In separation chamber, be provided with membrane separator, from the aerogenesis end of membrane separator, obtain hydrogen.
The hydrogen that [step 3] described hydrogen producer makes is delivered to membrane separation device and carries out separation, for separating of the difference of the inside and outside pressure of the membrane separation device of hydrogen, is more than or equal to 0.7M Pa;
In the present embodiment, hydrogen manufacturing subsystem is arranged at separation chamber on the top of reformer chamber, the temperature that middle part and bottom are compared in reformer chamber top is higher, by connecting line, connect reformer chamber and separation chamber, the gas that connecting line can utilize the high-temperature heating on reformer chamber top to carry in the process of carrying, play pre-heat effect, mode of heating is very convenient simultaneously.Pipeline between reformer chamber and separation chamber, as preheating temperature-controlling mechanism, can, to heating from the gas of reformer chamber output, make from the temperature of gas of reformer chamber output identical with the temperature of separation chamber or approaching; Thereby can guarantee respectively the low temperature requirement of reformer chamber catalyst, and the high temperature requirement of separation chamber, and then improve hydrogen preparation efficiency.
Embodiment tetra-
The difference of the present embodiment and embodiment tri-is, in the present embodiment, hydrogen manufacturing subsystem does not arrange solid hydrogen reservoir vessel 80, refers to Fig. 5, and hydrogen manufacturing subsystem comprises: liquid container 10, raw material conveying device 50, device for rapidly starting, hydrogen producer 20, membrane separation device 30.Described device for rapidly starting provides the startup energy for hydrogen producer; Described device for rapidly starting comprises the first starting drive 40, the second starting drive 60.
As shown in Figure 6, described the first starting drive 40 comprises that the internal diameter of housing 41, the first heating arrangements 42, the first gasification pipeline 43, the first gasification pipelines 43 is 1～2mm, and the first gasification pipeline 43 is closely wound on the first heating arrangements 42; The first heating arrangements 42 can be electrically heated rod, utilizes alternating current or storage battery, dry cell.
One end of described the first gasification pipeline 43 connects liquid container 10, and methyl alcohol is admitted in the first gasification pipeline 43; The other end of the first gasification pipeline 43 is exported vaporized methyl alcohol, then by ignition mechanism ignition; Or the other end of the first gasification pipeline 43 is exported vaporized methyl alcohol, and the methanol temperature of output reaches self-ignition point, methyl alcohol directly spontaneous combustion from the first gasification pipeline 43 outputs.
Described the second starting drive 60 comprises the second gasification pipeline, and the main body of the second gasification pipeline is arranged at described reformer chamber, the whole chamber heating (can also be other unit heating of hydrogen generating system) of attaching most importance to of the second gasification pipeline.The first gasification pipeline 43 is or/and the methyl alcohol of the second gasification pipeline output heats the second gasification pipeline when being reformer chamber heating, by the methanol gasifying in the second gasification pipeline.
First, methyl alcohol heating the second gasification pipeline that needs the first gasification pipeline 43 outputs, setting-up time after the second gasification pipeline can continue to produce the methyl alcohol gasifying, can select to close the first starting drive 40, and is the second gasification pipeline heating by the methyl alcohol of the second gasification pipeline output; Can further reduce the dependence to extra power like this.
Refer to Fig. 6, in order to improve the firing rate of hydrogen producer, at the reformer chamber inwall of described hydrogen producer 20, be provided with heating pipe line 21, in heating pipe line 21, be placed with catalyst (as can be by heating and temperature control at 380 ℃～480 ℃); Described device for rapidly starting 40, by heating described heating pipe line 21 for reformer chamber heats, can improve the efficiency of heating surface.
After described hydrogen generating system starts, the hydrogen that hydrogen generating system makes by hydrogen producer provides operation the required energy; Now, can close device for rapidly starting.
More than introduced the composition of methanol-water hydrogen generating system of the present invention, the present invention, when disclosing above-mentioned hydrogen generating system, also discloses a kind of hydrogen production process of above-mentioned methanol-water hydrogen generating system, and described method comprises the steps:
[step S1] be setting up procedure fast; Described hydrogen generating system utilizes device for rapidly starting to provide the startup energy to start.Specifically comprise:
The first heating arrangements energising setting-up time of the first starting drive, treats that the first heating arrangements reaches backward the first gasification pipeline of design temperature and passes into methyl alcohol; Because the first gasification pipeline is closely wound on the first heating arrangements, methanol temperature progressively raises; The first gasification pipeline is exported vaporized methyl alcohol, then by ignition mechanism ignition; Or the first gasification pipeline is exported vaporized methyl alcohol, and the methanol temperature of output reaches self-ignition point, methyl alcohol directly spontaneous combustion from the first gasification pipeline output;
The methyl alcohol of gasification is by burning heat release, for hydrogen producer provides the startup energy; Meanwhile, the methyl alcohol burning of the first gasification pipeline output is also the second gasification pipeline heating of the second starting drive, by the methanol gasifying in the second gasification pipeline;
After the methyl alcohol of output gasification in the second gasification pipeline, close the first starting drive, the methyl alcohol of being exported by the second gasification pipeline of the second starting drive is that reformer chamber heats, and heats the second gasification pipeline, by the methanol gasifying in the second gasification pipeline simultaneously; Described reformer chamber inwall is provided with heating pipe line, is placed with catalyst in heating pipe line; Described device for rapidly starting is that reformer chamber heats by heating described heating pipe line.
After [step S2] system starts, the hydrogen that hydrogen generating system makes by hydrogen producer provides operation the required energy; Treat that hydrogen generating system operation makes enough hydrogen, closes device for rapidly starting; The hydrogen partial being made by hydrogen producer is or/and residual air maintains hydrogen producer by burning moves.
In sum, instant hydrogen manufacturing electricity generation system and method that the present invention proposes, can collect the residual air that power generation sub-system is discharged, and therefrom extract hydrogen, oxygen, water, the heat release of can burning of hydrogen, oxygen, for power generation sub-system provides heat energy, water can transfer to hydrogen manufacturing subsystem and recycle, and system does not need extra water source.The present invention can raising system the efficiency of generating, save the energy.
Here description of the invention and application is illustrative, not wants by scope restriction of the present invention in the above-described embodiments.Here the distortion of disclosed embodiment and change is possible, and for those those of ordinary skill in the art, the various parts of the replacement of embodiment and equivalence are known.Those skilled in the art are noted that in the situation that not departing from spirit of the present invention or substantive characteristics, and the present invention can be with other form, structure, layout, ratio, and realizes with other assembly, material and parts.In the situation that not departing from the scope of the invention and spirit, can carry out other distortion and change to disclosed embodiment here.
Claims (7)
1. an instant hydrogen manufacturing electricity generation system, it is characterized in that, described system comprises: hydrogen manufacturing subsystem, air pressure adjustment subsystem, power generation sub-system, collection utilize subsystem, and hydrogen manufacturing subsystem, air pressure adjustment subsystem, power generation sub-system, collection utilize subsystem to connect successively;
Described hydrogen manufacturing subsystem utilizes methanol-water to prepare hydrogen, and described hydrogen manufacturing subsystem comprises solid hydrogen reservoir vessel, liquid container, raw material conveying device, hydrogen producer, membrane separation device;
Described hydrogen producer comprises heat exchanger, vaporizer, reformer chamber; Membrane separation device is arranged at the inside that Nei， separation chamber, separation chamber is arranged at reformer chamber;
Described solid hydrogen reservoir vessel, liquid container are connected with hydrogen producer respectively; In liquid container, store liquid first alcohol and water;
In described solid hydrogen reservoir vessel, store solid hydrogen, when hydrogen generating system starts, by gasification module, solid hydrogen is converted to gaseous hydrogen, gaseous hydrogen is by burning heat release, for hydrogen producer provides startup heat energy, as the startup energy of hydrogen producer;
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 reformer chamber is provided with catalyst, and reformer chamber bottom and middle part temperature are 300 ℃～420 ℃;
The temperature on described reformer chamber top is 400 ℃～570 ℃; Reformer chamber is connected by connecting line with separation chamber, and heating can be continued from the gas of reformer chamber output in all or part of top that is arranged at reformer chamber of connecting line by the high temperature on reformer chamber top; Described connecting line, as the buffering between reformer chamber and separation chamber, makes from the temperature of gas of reformer chamber output identical with the temperature of separation chamber or approaching;
Temperature Setting in described separation chamber is 350 ℃～570 ℃; In separation chamber, be provided with membrane separator, from the aerogenesis end of membrane separator, obtain hydrogen;
Described raw material conveying device provides power, and the raw material in liquid container is delivered to hydrogen producer; Described raw material conveying device provides the pressure of 0.15～5MPa to raw material, make the hydrogen that hydrogen producer makes have enough pressure;
Described hydrogen producer starts after hydrogen manufacturing, and the hydrogen partial that hydrogen producer makes is or/and residual air maintains hydrogen producer by burning moves;
The hydrogen that described hydrogen producer makes is delivered to membrane separation device and carries out separation, for separating of the difference of the inside and outside pressure of the membrane separation device of hydrogen, is more than or equal to 0.7M Pa;
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 passes through transfer conduit real-time Transmission to power generation sub-system by the hydrogen making; Described transfer conduit is provided with air pressure adjustment subsystem, for adjusting the air pressure of transfer conduit; The hydrogen gas generation that described power generation sub-system utilizes hydrogen manufacturing subsystem to make;
Described air pressure adjustment subsystem comprises microprocessor, gas pressure sensor, valve positioner, air outlet valve, outlet pipe; Described gas pressure sensor is arranged in transfer conduit, in order to respond to the barometric information in transfer conduit, and the barometric information of induction is sent to microprocessor; Described microprocessor is compared this barometric information receiving from gas pressure sensor and setting threshold interval; When the maximum of the pressure data receiving higher than setting threshold interval, microprocessor by-pass valve control controller opens air outlet valve setting-up time, make in transfer conduit air pressure in setting range, one end of outlet pipe connects air outlet valve simultaneously, the other end connects described hydrogen manufacturing subsystem, and the firing equipment that needs that is hydrogen manufacturing subsystem by burning heats; When the minimum value of the pressure data receiving lower than setting threshold interval, microprocessor is controlled the transporting velocity that described hydrogen manufacturing subsystem is accelerated raw material;
Described collection utilizes subsystem to connect the exhaust passage outlet of power generation sub-system, from the gas of discharging, collects water, utilizes the water collected as the raw material of hydrogen manufacturing subsystem, thereby recycles;
Described collection utilizes subsystem to comprise hydrogen separator, hydrogen check-valves, oxygen separator, oxygen check valve, hydrogen is separated with water, oxygen is separated with water.
2. an instant hydrogen manufacturing electricity generation system, is characterized in that, described system comprises: hydrogen manufacturing subsystem, power generation sub-system, collection utilize subsystem, and hydrogen manufacturing subsystem, power generation sub-system, collection utilize subsystem to connect successively;
Described hydrogen manufacturing subsystem utilizes methanol-water to prepare hydrogen, by the hydrogen making by transfer conduit real-time Transmission to power generation sub-system for generating;
Described collection utilizes subsystem to connect the exhaust passage outlet of power generation sub-system, collects water, maybe by the raw material of the water hydrogen manufacturing subsystem of collecting from the gas of discharging.
3. instant hydrogen manufacturing electricity generation system according to claim 2, is characterized in that:
Described collection utilizes subsystem to comprise air-water separator, the water of collecting is delivered to hydrogen manufacturing subsystem, thereby recycles.
4. instant hydrogen manufacturing electricity generation system according to claim 2, is characterized in that:
Described collection utilizes subsystem to comprise hydrogen separator, hydrogen check-valves, and the exhaust passage outlet of power generation sub-system connects the entrance of hydrogen separator, in the pipeline that hydrogen separator exit connects, is provided with hydrogen check-valves; Described hydrogen separator is for separating of hydrogen and water.
5. instant hydrogen manufacturing electricity generation system according to claim 3, is characterized in that:
Described collection utilizes subsystem also to comprise hydrogen/oxygen separator, for separating of hydrogen and oxygen; Hydrogen/oxygen separator is arranged between the outlet of described power generation sub-system exhaust passage and hydrogen separator.
6. instant hydrogen manufacturing electricity generation system according to claim 2, is characterized in that:
Described collection utilizes subsystem to comprise oxygen separator, oxygen check valve, for collecting oxygen;
Described collection utilize hydrogen that subsystem collects and oxygen for hydrogen manufacturing subsystem or/and power generation sub-system.
7. a preparing hydrogen, generating power method for the described system of one of claim 1 to 6, is characterized in that, described preparing hydrogen, generating power method comprises the steps:
Described hydrogen manufacturing subsystem utilizes methanol-water to prepare hydrogen, and the hydrogen making is passed through to transfer conduit real-time Transmission to power generation sub-system;
The hydrogen gas generation that described power generation sub-system utilizes hydrogen manufacturing subsystem to make;
Described collection utilizes subsystem to connect the exhaust passage outlet of power generation sub-system, collects water, maybe by the raw material of the water hydrogen manufacturing subsystem of collecting from the gas of discharging.
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