CN103569964A - Equipment for preparing hydrogen from methanol and water - Google Patents
Equipment for preparing hydrogen from methanol and water Download PDFInfo
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- CN103569964A CN103569964A CN201310524567.4A CN201310524567A CN103569964A CN 103569964 A CN103569964 A CN 103569964A CN 201310524567 A CN201310524567 A CN 201310524567A CN 103569964 A CN103569964 A CN 103569964A
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Abstract
The invention discloses equipment for preparing hydrogen from methanol and water. The equipment comprises a liquid storage container, a raw material conveying device, hydrogen production equipment, a film separation device and a tail gas heat exchange device, wherein the liquid storage container is used for storing liquid methanol and water; the raw material conveying device is used for conveying the raw materials, namely, methanol and water, in the liquid storage container to the hydrogen production equipment so as to produce hydrogen; the produced hydrogen is conveyed to the film separation device to be separated; the tail gas heat exchange device comprises a second heat exchanger; the second heat exchanger takes the raw materials, namely, methanol and water, as cooling mediums to cool down a tail gas; an inlet of a heat exchange tube of the second heat exchanger is connected with the liquid storage container through a pipeline; an outlet of the heat exchange tube of the second heat exchanger is connected with the hydrogen production equipment; the temperature of the raw materials is raised through heat exchange of the heat exchange tube of the second heat exchanger, and meanwhile the temperature of the tail gas is reduced. Due to adoption of the equipment for preparing hydrogen from methanol water, a waste gas treatment device does not need to be arranged, so that the size of the equipment is reduced, and the mobility of the equipment is improved.
Description
Technical field
The invention belongs to technical field of hydrogen preparation, relate to a kind of equipment of preparing hydrogen, relate in particular to a kind of equipment that utilizes methanol-water to prepare hydrogen.
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 carbonic acid gas and sulfurous gas, 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 thermal value.The weight of hydrogen is light especially, and it is all gently more than gasoline, Sweet 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, Sweet 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, 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.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 geseous 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 liquid 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 automobile fuel, not only clean with hydrogen, easily start at low temperatures, and little to the corrosive nature of engine, can extend the work-ing 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 motor car 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 launch vehicle that number spaceship and China launch a man-made satellite., all with liquid 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 undersea boat, 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 Sweet natural gas, and this must consume original just mineral 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 novel 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
2mixed gas, through further aftertreatment, can obtain hydrogen and carbon dioxide gas simultaneously.
Methyl alcohol and water vapour pass through catalyzer under certain temperature, pressure condition, under the effect of catalyzer, the transformationreation of methanol decomposition reaction and carbon monoxide occurs, generate hydrogen and carbonic acid gas, 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 palladium membrane sepn by H
2and CO
2separation, obtains high-purity hydrogen.The power consumption of pressure swing adsorption process is high, equipment is large, and is not suitable for small-scale hydrogen preparation.
In addition, existing hydrogen producer, because the temperature of waste gas is higher, need to arrange waste gas output channel discharging waste gas conventionally.The setting of waste gas output channel has not only increased the volume of equipment, not portable, has the risk of scalding people simultaneously.
In view of this, nowadays in the urgent need to designing a kind of new hydrogen producer, to overcome the above-mentioned defect of existing hydrogen producer.
Summary of the invention
Technical problem to be solved by this invention is: a kind of equipment that utilizes methanol-water to prepare hydrogen is provided, emission-control equipment can be set, thereby reduces equipment volume, improve movability.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
Utilize methanol-water to prepare an equipment for hydrogen, described equipment comprises: solid hydrogen storage vessel, liquid container, raw material conveying device, hydrogen producer, membrane separation unit, tail gas heat-exchanger rig;
Described liquid container is for storing liquid first alcohol and water, and raw material conveying device is delivered to hydrogen producer by the first alcohol and water raw material in described liquid container and prepares hydrogen, and the hydrogen making is delivered to membrane separation unit and carries out separation;
Described tail gas heat-exchanger rig comprises the second interchanger, and it is heat-eliminating medium cooled exhaust gas that the second interchanger be take material benzenemethanol and water; The entrance of the heat transfer tube of the second interchanger connects liquid container by pipeline, and the outlet of the heat transfer tube of the second interchanger connects hydrogen producer; Raw material is raise by temperature through the heat exchange of the second heat exchanger heat-exchanging tube, and the temperature of tail gas reduces simultaneously;
Described hydrogen producer comprises interchanger, vaporizer, reformer chamber; Membrane separation unit is arranged at the top that Nei， separate chamber, separate chamber is arranged at reformer chamber;
Described solid hydrogen storage vessel, liquid container are connected with hydrogen producer respectively; In liquid container, store liquid first alcohol and water;
In described solid hydrogen storage vessel, store solid hydrogen, when hydrogen producer 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 interchanger heat exchange by raw material conveying device, enters vaporizer gasification after heat exchange;
Methanol vapor and water vapour after gasification enter reformer chamber, and reformer chamber is provided with catalyzer, 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 pipeline with separate 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 pipeline by the high temperature on reformer chamber top; Described connecting pipeline, as the buffering between reformer chamber and separate chamber, makes from the temperature of gas of reformer chamber output identical with the temperature of separate chamber or approaching;
Temperature Setting in described separate chamber is 400 ℃～570 ℃; In separate chamber, be provided with membrane separation apparatus, from the aerogenesis end of membrane separation apparatus, 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 1.1～5M Pa 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 unit and carries out separation, for separating of the difference of the inside and outside pressure of the membrane separation unit of hydrogen, is more than or equal to 1.1M Pa;
Described membrane separation unit is the membrane separation unit at porous ceramic surface Vacuum Deposition palladium-silver alloy, and coatings is palladium-silver alloy, and the mass percent palladium of palladium-silver alloy accounts for 75%～78%, and silver accounts for 22%～25%.
Utilize methanol-water to prepare an equipment for hydrogen, described equipment comprises: liquid container, raw material conveying device, hydrogen producer, membrane separation unit, tail gas heat-exchanger rig;
Described liquid container is for storing liquid first alcohol and water, and raw material conveying device is delivered to hydrogen producer by the first alcohol and water raw material in described liquid container and prepares hydrogen, and the hydrogen making is delivered to membrane separation unit and carries out separation;
Described tail gas heat-exchanger rig comprises the second interchanger, and it is heat-eliminating medium cooled exhaust gas that the second interchanger be take material benzenemethanol and water; The entrance of the heat transfer tube of the second interchanger connects liquid container by pipeline, and the outlet of the heat transfer tube of the second interchanger connects hydrogen producer; Raw material is raise by temperature through the heat exchange of the second heat exchanger heat-exchanging tube, and the temperature of tail gas reduces simultaneously.
As a preferred embodiment of the present invention, described membrane separation unit is the membrane separation unit at porous ceramic surface Vacuum Deposition palladium-silver alloy, and coatings is palladium-silver alloy, and the mass percent palladium of palladium-silver alloy accounts for 75%～78%, and silver accounts for 22%～25%.
As a preferred embodiment of the present invention, described equipment comprises interchanger, vaporizer, reformer chamber; Membrane separation unit is arranged at the top that Nei， separate chamber, separate chamber is arranged at reformer chamber;
Described solid hydrogen storage vessel, liquid container are connected with hydrogen producer respectively; In liquid container, store liquid first alcohol and water;
In described solid hydrogen storage vessel, store solid hydrogen, when hydrogen producer 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 interchanger heat exchange by raw material conveying device, enters vaporizer gasification after heat exchange.
As a preferred embodiment of the present invention, methanol vapor and water vapour after gasification enter reformer chamber, and reformer chamber is provided with catalyzer, 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 pipeline with separate 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 pipeline by the high temperature on reformer chamber top; Described connecting pipeline, as the buffering between reformer chamber and separate chamber, makes from the temperature of gas of reformer chamber output identical with the temperature of separate chamber or approaching;
Temperature Setting in described separate chamber is 400 ℃～570 ℃; In separate chamber, be provided with membrane separation apparatus, from the aerogenesis end of membrane separation apparatus, obtain hydrogen.
As a preferred embodiment of the present invention, 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 1.1～5M Pa 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 unit and carries out separation, for separating of the difference of the inside and outside pressure of the membrane separation unit of hydrogen, is more than or equal to 1.1M Pa;
As a preferred embodiment of the present invention, described tail gas heat-exchanger rig also comprises ventilating fan.
Beneficial effect of the present invention is: the methanol-water that utilizes that the present invention proposes is prepared the equipment of hydrogen, emission-control equipment can be set, thereby reduce equipment volume, improves movability.Meanwhile, through the material temperature rising (raw material needs heating when preparing hydrogen) of interchanger, thereby can effectively reduce hydrogen manufacturing cost.In addition, present device can also be improved environment.
Accompanying drawing explanation
Fig. 1 is the composition schematic diagram of the equipment that in embodiment mono-, the present invention prepares hydrogen.
Fig. 2 is the structural representation of tail gas heat-exchanger rig.
Fig. 3 is the composition schematic diagram of the equipment that in embodiment bis-, the present invention prepares hydrogen.
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 equipment that utilizes methanol-water to prepare hydrogen, and described equipment comprises: liquid container 10, raw material conveying device 50, hydrogen producer 20, membrane separation unit 30, tail gas heat-exchanger rig 60.Described liquid container 10 is for storing liquid first alcohol and water, and raw material conveying device 50 is delivered to hydrogen producer 20 by the first alcohol and water raw material in described liquid container 10 and prepares hydrogen, and the hydrogen making is delivered to membrane separation unit 30 and carries out separation.
Described tail gas heat-exchanger rig 60 comprises the second interchanger, and it is heat-eliminating medium cooled exhaust gas that the second interchanger be take material benzenemethanol and water; The entrance of the heat transfer tube of the second interchanger connects liquid container by pipeline, and the outlet of the heat transfer tube of the second interchanger connects hydrogen producer 20; Raw material is raise by temperature through the heat exchange of the second heat exchanger heat-exchanging tube, and the temperature of tail gas reduces simultaneously.
In the present embodiment, the structure of tail gas heat-exchanger rig as shown in Figure 2, is provided with space separating board in tail gas heat-exchanger rig, makes air-flow walk broken line, can play better heat transfer effect.
In addition, tail gas heat-exchanger rig also comprises ventilating fan, for driving exhaust-gas flow, thereby improves off gas treatment speed.
Embodiment bis-
The difference of the present embodiment and embodiment mono-is, in the present embodiment, refer to Fig. 3, the described equipment utilization methanol-water of preparing hydrogen is prepared hydrogen, and the described equipment of preparing hydrogen comprises solid hydrogen storage vessel 40, liquid container 10, raw material conveying device 50, hydrogen producer 20, membrane separation unit 30, tail gas heat-exchanger rig 60.Tail gas heat-exchanger rig 60 is similar with embodiment mono-.
Described solid hydrogen storage vessel 40, liquid container 10 are connected with hydrogen producer 20 respectively; In liquid container 10, store liquid first alcohol and water, in described solid hydrogen storage vessel 40, store solid hydrogen.
When hydrogen generating system starts, by gasification module, the solid hydrogen in solid hydrogen storage vessel 40 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 storage vessel 40 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 1.1M Pa or 1.2M Pa or 1.5M Pa or 5M Pa pressure) of 1.1～5M 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 unit 30 and carries out separation, for separating of the difference of the inside and outside pressure of the membrane separation unit 30 of hydrogen be more than or equal to 1.1M Pa(as the inside and outside pressure of membrane separation unit 30 be 1.1M Pa or 1.2M Pa or 1.5M Pa or 5M Pa).
In the present embodiment, described membrane separation unit 30 is the membrane separation unit at porous ceramic surface Vacuum Deposition palladium-silver alloy, and coatings is palladium-silver alloy, and the mass percent palladium of palladium-silver alloy accounts for 75%～78%, and silver accounts for 22%～25%.The preparation technology of described membrane separation unit 30 comprises the steps:
Step 1, porous ceramics 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 noble metal, and described noble metal is palladium-silver alloy, 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 when the indoor vacuum tightness of vacuum is less than 10-2Pa, is filled with the argon gas of setting concentration in vacuum chamber;
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 noble 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 interchanger, vaporizer, reformer chamber; Membrane separation unit is arranged at the top that Nei， separate chamber, separate chamber is arranged at reformer chamber.
First alcohol and water in described liquid container is delivered to interchanger heat exchange by raw material conveying device, enters vaporizer gasification after heat exchange; Methanol vapor and water vapour after gasification enter reformer chamber, and reformer chamber is provided with catalyzer, 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 pipeline with separate 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 pipeline by the high temperature on reformer chamber top; Described connecting pipeline, as the buffering between reformer chamber and separate chamber, makes from the temperature of gas of reformer chamber output identical with the temperature of separate chamber or approaching; Temperature Setting in described separate chamber is 400 ℃～570 ℃; In separate chamber, be provided with membrane separation apparatus, from the aerogenesis end of membrane separation apparatus, obtain hydrogen.
More than introduced methanol-water and prepared the composition of the equipment of hydrogen, the present invention also discloses a kind of hydrogen production process that utilizes above-mentioned methanol-water to prepare the equipment of hydrogen, and described hydrogen production process comprises:
In [step 0] described solid hydrogen storage 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 1.1～5M 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 interchanger heat exchange by raw material conveying device, enters vaporizer gasification after heat exchange;
Methanol vapor and water vapour after gasification enter reformer chamber, and reformer chamber is provided with catalyzer, 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 pipeline with separate 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 pipeline by the high temperature on reformer chamber top; Described connecting pipeline, as the buffering between reformer chamber and separate chamber, makes from the temperature of gas of reformer chamber output identical with the temperature of separate chamber or approaching;
Temperature Setting in described separate chamber is 400 ℃～570 ℃; In separate chamber, be provided with membrane separation apparatus, from the aerogenesis end of membrane separation apparatus, obtain hydrogen.
The hydrogen that [step 3] described hydrogen producer makes is delivered to membrane separation unit and carries out separation, for separating of the difference of the inside and outside pressure of the membrane separation unit of hydrogen, is more than or equal to 1.1M Pa;
In the present embodiment, the equipment of preparing hydrogen is arranged at separate chamber on the top of reformer chamber, the temperature that middle part and bottom are compared in reformer chamber top is higher, by connecting pipeline, connect reformer chamber and separate chamber, the gas that connecting pipeline can utilize the heat on reformer chamber top to carry in the process of carrying, play pre-heat effect, type of heating is very convenient simultaneously.Pipeline between reformer chamber and separate chamber, as preheating temperature control 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 separate chamber or approaching; Thereby can guarantee respectively the low temperature requirement of reformer chamber catalyzer, and the high temperature requirement of separate chamber, and then improve hydrogen preparation efficiency.
In sum, the methanol-water that utilizes that the present invention proposes is prepared the equipment of hydrogen, emission-control equipment can be set, thereby reduce equipment volume, improves movability.Meanwhile, through the material temperature rising (raw material needs heating when preparing hydrogen) of interchanger, thereby can effectively reduce hydrogen manufacturing cost.In addition, present device can also be improved environment.
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 essential characteristic, 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 (8)
1. utilize methanol-water to prepare an equipment for hydrogen, it is characterized in that, described equipment comprises: solid hydrogen storage vessel, liquid container, raw material conveying device, hydrogen producer, membrane separation unit, tail gas heat-exchanger rig;
Described liquid container is for storing liquid first alcohol and water, and raw material conveying device is delivered to hydrogen producer by the first alcohol and water raw material in described liquid container and prepares hydrogen, and the hydrogen making is delivered to membrane separation unit and carries out separation;
Described tail gas heat-exchanger rig comprises the second interchanger, and it is heat-eliminating medium cooled exhaust gas that the second interchanger be take material benzenemethanol and water; The entrance of the heat transfer tube of the second interchanger connects liquid container by pipeline, and the outlet of the heat transfer tube of the second interchanger connects hydrogen producer; Raw material is raise by temperature through the heat exchange of the second heat exchanger heat-exchanging tube, and the temperature of tail gas reduces simultaneously;
Described hydrogen producer comprises interchanger, vaporizer, reformer chamber; Membrane separation unit is arranged at the top that Nei， separate chamber, separate chamber is arranged at reformer chamber;
Described solid hydrogen storage vessel, liquid container are connected with hydrogen producer respectively; In liquid container, store liquid first alcohol and water;
In described solid hydrogen storage vessel, store solid hydrogen, when hydrogen producer 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 interchanger heat exchange by raw material conveying device, enters vaporizer gasification after heat exchange;
Methanol vapor and water vapour after gasification enter reformer chamber, and reformer chamber is provided with catalyzer, 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 pipeline with separate 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 pipeline by the high temperature on reformer chamber top; Described connecting pipeline, as the buffering between reformer chamber and separate chamber, makes from the temperature of gas of reformer chamber output identical with the temperature of separate chamber or approaching;
Temperature Setting in described separate chamber is 400 ℃～570 ℃; In separate chamber, be provided with membrane separation apparatus, from the aerogenesis end of membrane separation apparatus, 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 1.1～5M Pa 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 unit and carries out separation, for separating of the difference of the inside and outside pressure of the membrane separation unit of hydrogen, is more than or equal to 1.1M Pa;
Described membrane separation unit is the membrane separation unit at porous ceramic surface Vacuum Deposition palladium-silver alloy, and coatings is palladium-silver alloy, and the mass percent palladium of palladium-silver alloy accounts for 75%～78%, and silver accounts for 22%～25%.
2. utilize methanol-water to prepare an equipment for hydrogen, it is characterized in that, described equipment comprises: liquid container, raw material conveying device, hydrogen producer, membrane separation unit, tail gas heat-exchanger rig;
Described liquid container is for storing liquid first alcohol and water, and raw material conveying device is delivered to hydrogen producer by the first alcohol and water raw material in described liquid container and prepares hydrogen, and the hydrogen making is delivered to membrane separation unit and carries out separation;
Described tail gas heat-exchanger rig comprises the second interchanger, and it is heat-eliminating medium cooled exhaust gas that the second interchanger be take material benzenemethanol and water; The entrance of the heat transfer tube of the second interchanger connects liquid container by pipeline, and the outlet of the heat transfer tube of the second interchanger connects hydrogen producer; Raw material is raise by temperature through the heat exchange of the second heat exchanger heat-exchanging tube, and the temperature of tail gas reduces simultaneously.
3. the equipment that utilizes methanol-water to prepare hydrogen according to claim 2, is characterized in that:
Described membrane separation unit is the membrane separation unit at porous ceramic surface Vacuum Deposition palladium-silver alloy, and coatings is palladium-silver alloy, and the mass percent palladium of palladium-silver alloy accounts for 75%～78%, and silver accounts for 22%～25%.
4. the equipment that utilizes methanol-water to prepare hydrogen according to claim 2, is characterized in that:
Described equipment comprises interchanger, vaporizer, reformer chamber; Membrane separation unit is arranged at the top that Nei， separate chamber, separate chamber is arranged at reformer chamber;
Described liquid container is connected with hydrogen producer; In liquid container, store liquid first alcohol and water;
First alcohol and water in described liquid container is delivered to interchanger heat exchange by raw material conveying device, enters vaporizer gasification after heat exchange.
5. the equipment that utilizes methanol-water to prepare hydrogen according to claim 4, is characterized in that:
Described equipment also comprises solid hydrogen storage vessel, in solid hydrogen storage vessel, store solid hydrogen, when hydrogen producer 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.
6. the equipment that utilizes methanol-water to prepare hydrogen according to claim 4, is characterized in that:
Methanol vapor and water vapour after gasification enter reformer chamber, and reformer chamber is provided with catalyzer, 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 pipeline with separate 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 pipeline by the high temperature on reformer chamber top; Described connecting pipeline, as the buffering between reformer chamber and separate chamber, makes from the temperature of gas of reformer chamber output identical with the temperature of separate chamber or approaching;
Temperature Setting in described separate chamber is 400 ℃～570 ℃; In separate chamber, be provided with membrane separation apparatus, from the aerogenesis end of membrane separation apparatus, obtain hydrogen.
7. the equipment that utilizes methanol-water to prepare hydrogen according to claim 4, is characterized in that:
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 1.1～5M Pa 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 unit and carries out separation, for separating of the difference of the inside and outside pressure of the membrane separation unit of hydrogen, is more than or equal to 1.1M Pa.
8. the equipment that utilizes methanol-water to prepare hydrogen according to claim 2, is characterized in that:
Described tail gas heat-exchanger rig also comprises ventilating fan.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310524567.4A CN103569964B (en) | 2013-10-29 | 2013-10-29 | Methanol-water is utilized to prepare the equipment of hydrogen |
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| CN103864017A (en) * | 2014-02-26 | 2014-06-18 | 上海合既得动氢机器有限公司 | Small-size methanol water hydrogen production equipment and hydrogen production method |
| CN104860264A (en) * | 2015-04-22 | 2015-08-26 | 广东合即得能源科技有限公司 | Residual gas heat exchange combustion-supporting system and method based on methanol water reforming hydrogen production system |
| CN104925755A (en) * | 2015-06-05 | 2015-09-23 | 广东合即得能源科技有限公司 | Hydrogen purification device protection system and method based on methanol water reforming hydrogen production system |
| CN105329853A (en) * | 2015-11-06 | 2016-02-17 | 江门市宏乔新材料科技有限公司江海区分公司 | Portable mobile hydrogen making machine based on principle of making hydrogen through methyl alcohol water |
| CN107055470A (en) * | 2017-03-10 | 2017-08-18 | 同济大学 | A kind of hot utilization system of liquid organic hydrogen storage carrier reactor |
| US9950912B2 (en) | 2014-05-26 | 2018-04-24 | Xuzhou Heavy Machinery Co., Ltd. | Combined counterweight hitching device and method thereof, and counterweight mounting structure |
| CN110790233A (en) * | 2019-10-28 | 2020-02-14 | 中科液态阳光(苏州)氢能科技发展有限公司 | Membrane separation purification device heat exchange system for methanol-water hydrogenation station |
| CN111467913A (en) * | 2020-03-27 | 2020-07-31 | 大连海奥膜技术有限公司 | Comprehensive recycling process and equipment for refinery tail gas |
| CN114620678A (en) * | 2020-12-10 | 2022-06-14 | 广东醇氢新能源研究院有限公司 | Hydrogen production system and hydrogen production method |
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| CN103864017A (en) * | 2014-02-26 | 2014-06-18 | 上海合既得动氢机器有限公司 | Small-size methanol water hydrogen production equipment and hydrogen production method |
| US9950912B2 (en) | 2014-05-26 | 2018-04-24 | Xuzhou Heavy Machinery Co., Ltd. | Combined counterweight hitching device and method thereof, and counterweight mounting structure |
| CN104860264A (en) * | 2015-04-22 | 2015-08-26 | 广东合即得能源科技有限公司 | Residual gas heat exchange combustion-supporting system and method based on methanol water reforming hydrogen production system |
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| CN104925755B (en) * | 2015-06-05 | 2017-06-06 | 广东合即得能源科技有限公司 | Hydrogen purification devices protection system and method based on methanol-water hydrogen production system employing reforming technology |
| CN105329853A (en) * | 2015-11-06 | 2016-02-17 | 江门市宏乔新材料科技有限公司江海区分公司 | Portable mobile hydrogen making machine based on principle of making hydrogen through methyl alcohol water |
| CN107055470A (en) * | 2017-03-10 | 2017-08-18 | 同济大学 | A kind of hot utilization system of liquid organic hydrogen storage carrier reactor |
| CN110790233A (en) * | 2019-10-28 | 2020-02-14 | 中科液态阳光(苏州)氢能科技发展有限公司 | Membrane separation purification device heat exchange system for methanol-water hydrogenation station |
| CN111467913A (en) * | 2020-03-27 | 2020-07-31 | 大连海奥膜技术有限公司 | Comprehensive recycling process and equipment for refinery tail gas |
| CN114620678A (en) * | 2020-12-10 | 2022-06-14 | 广东醇氢新能源研究院有限公司 | Hydrogen production system and hydrogen production method |
| CN114620677A (en) * | 2020-12-10 | 2022-06-14 | 广东醇氢新能源研究院有限公司 | Hydrogen production system |
| CN114620678B (en) * | 2020-12-10 | 2023-10-27 | 广东醇氢新能源研究院有限公司 | Hydrogen production system and hydrogen production method |
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