CN103613069A - Methanol water hydrogen production system and method capable of rapidly starting - Google Patents
Methanol water hydrogen production system and method capable of rapidly starting Download PDFInfo
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- CN103613069A CN103613069A CN201310576442.6A CN201310576442A CN103613069A CN 103613069 A CN103613069 A CN 103613069A CN 201310576442 A CN201310576442 A CN 201310576442A CN 103613069 A CN103613069 A CN 103613069A
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Abstract
The invention discloses a methanol water hydrogen production system and a method capable of rapidly starting. The system comprises a liquid storage container, a raw material conveying device, a rapid starting device, hydrogen production equipment and a membrane separation device, wherein the rapid starting device comprises a heating mechanism and a gasifying pipeline which is wound on the heating mechanism; one end of the gasifying pipeline is connected to the liquid storage container to feed methanol into the gasifying pipeline, and the other end outputs gasified methanol and then ignites to burn the methanol through an igniting mechanism; or the other end of the gasifying pipeline outputs gasified methanol that achieves a spontaneous ignition point, and the methanol gets to direct spontaneous ignition after being outputted from the gasifying pipeline; and the rapid starting device is used for providing starting power to the hydrogen production equipment. The methanol water hydrogen production system capable of rapidly starting provided by the invention can rapidly start without 10min generally; meanwhile, the hydrogen production system can gasify the methanol through a heating bar by electric energy, so as to reduce energy consumption, and 2 batteries are enough generally.
Description
Technical field
The invention belongs to technical field of hydrogen preparation, relate to a kind of hydrogen generating system, relate in particular to a kind of methanol-water hydrogen generating system that can start fast; Meanwhile, the invention still further relates to a kind of methanol-water hydrogen production process that can start fast.
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.
Existing hydrogen producer, cold start-up needs for a long time conventionally, and generally at least more than 5 hours, some equipment even needs 1 day time to start.And warm start need to expend mass energy, make the equipment such as reformer chamber (conventionally needing more than 400 ℃) in the condition of high temperature.
Therefore, how to make hydrogen producer not only realize quick cold start-up, but also can guarantee that save energy (also needing practical) is the urgent problems that solve of current industry needs.
Summary of the invention
Technical problem to be solved by this invention is: a kind of methanol-water hydrogen generating system that can start is fast provided, and capable of fast starting, power consumption is few, practical simultaneously.
In addition, the present invention also provides a kind of methanol-water hydrogen production process that can start fast, hydrogen manufacturing capable of fast starting, and power consumption is few, practical simultaneously.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
The methanol-water hydrogen generating system that can start fast, described system comprises: liquid container, raw material conveying device, device for rapidly starting, hydrogen producer, membrane separation unit;
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 liquid container is connected with hydrogen producer; In liquid container, store liquid first alcohol and water;
Described system utilizes device for rapidly starting to provide the startup energy to start; Device for rapidly starting comprises heating arrangements, gasification pipeline, and the internal diameter of gasification pipeline is 1～2mm, and gasification pipeline is closely wound on heating arrangements; One end of described gasification pipeline connects liquid container, and methyl alcohol is sent in gasification pipeline; The other end of gasification pipeline is exported vaporized methyl alcohol, then by ignition mechanism ignition; Or the other end of gasification pipeline is exported vaporized methyl alcohol, and the methanol temperature of output reaches spontaneous ignition temperature, methyl alcohol directly spontaneous combustion from the output of gasification pipeline; Described device for rapidly starting provides the startup energy for hydrogen producer; Described reformer chamber inwall is provided with heating pipe line, is placed with catalyzer in heating pipe line; Described device for rapidly starting is that reformer chamber heats by heating described heating pipe line;
After described hydrogen generating system starts, the hydrogen that hydrogen generating system makes by hydrogen producer provides operation the required energy;
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 300 ℃～420 ℃;
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 350 ℃～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 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 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 0.7MPa;
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%.
The methanol-water hydrogen generating system that can start fast, described system comprises: liquid container, raw material conveying device, device for rapidly starting, hydrogen producer, membrane separation unit;
Described device for rapidly starting comprises heating arrangements, gasification pipeline, and gasification pipeline is wound on heating arrangements;
One end of described gasification pipeline connects liquid container, and methyl alcohol is sent in gasification pipeline; The other end of gasification pipeline is exported vaporized methyl alcohol, then by ignition mechanism ignition; Or the other end of gasification pipeline is exported vaporized methyl alcohol, and the methanol temperature of output reaches spontaneous ignition temperature, methyl alcohol directly spontaneous combustion from the output of gasification pipeline; Described device for rapidly starting provides the startup energy for hydrogen producer.
As a preferred embodiment of the present invention, described hydrogen producer comprises reformer chamber, and reformer chamber inwall is provided with heating pipe line, is placed with catalyzer in heating pipe line; Described device for rapidly starting is that reformer chamber heats by heating described heating pipe line.
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 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 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 0.7MPa.
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 heating arrangements is electrically heated rod.
A hydrogen production process for above-mentioned methanol-water hydrogen generating system, described method comprises the steps:
Step S1, quick setting up procedure; Described hydrogen generating system utilizes device for rapidly starting to provide the startup energy to start; Specifically comprise:
Heating arrangements energising setting-up time, mechanism to be heated reaches the backward gasification pipeline of design temperature and passes into methyl alcohol; Because gasification pipeline is closely wound on heating arrangements, methanol temperature progressively raises; Gasification pipeline is exported vaporized methyl alcohol, then by ignition mechanism ignition; Or gasification pipeline is exported vaporized methyl alcohol, and the methanol temperature of output reaches spontaneous ignition temperature, methyl alcohol directly spontaneous combustion from the output of gasification pipeline;
The methyl alcohol of gasification is by burning heat release, for hydrogen producer provides the startup energy; Described reformer chamber inwall is provided with heating pipe line, is placed with catalyzer in heating pipe line; Described device for rapidly starting is that reformer chamber heats by heating described heating pipe line;
After step S2, system start, the hydrogen that hydrogen generating system makes by hydrogen producer provides operation the required energy; Treat that hydrogen generating system operation makes enough hydrogen, close device for rapidly starting, the hydrogen partial being made by hydrogen producer is or/and residual air maintains hydrogen producer by burning moves; Hydrogen production process specifically comprises:
First alcohol and water in described liquid container is delivered to the interchanger heat exchange of hydrogen producer by raw material conveying device, enter 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 300 ℃～420 ℃;
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 350 ℃～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 0.15～5MPa to raw material, make the hydrogen that hydrogen producer makes have enough pressure; 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 0.7MPa; 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%;
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.
A hydrogen production process for above-mentioned methanol-water hydrogen generating system, described method comprises the steps:
Step S1, quick setting up procedure; Described hydrogen generating system utilizes device for rapidly starting to provide the startup energy to start; Specifically comprise:
Gasification pipeline passes into methyl alcohol, and methyl alcohol is by heating arrangements heating and gasifying;
Gasification pipeline is exported vaporized methyl alcohol, then by ignition mechanism ignition; Or gasification pipeline is exported vaporized methyl alcohol, and the methanol temperature of output reaches spontaneous ignition temperature, methyl alcohol directly spontaneous combustion from the output of gasification pipeline;
Vaporized methyl alcohol is by burning heat release, for hydrogen producer provides the startup energy.
As a preferred embodiment of the present invention, in described step S1, heating arrangements is electrically heated rod, energising setting-up time, and mechanism to be heated reaches the backward gasification pipeline of design temperature and passes into methyl alcohol; Because gasification pipeline is closely wound on heating arrangements, methanol temperature progressively raises, until gasification; Described reformer chamber inwall is provided with heating pipe line, is placed with catalyzer in heating pipe line; Described device for rapidly starting is that reformer chamber heats by heating described heating pipe line.
As a preferred embodiment of the present invention, described hydrogen production process also comprises step S2: after 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, close device for rapidly starting, the hydrogen partial being made by hydrogen producer is or/and residual air maintains hydrogen producer by burning moves; Hydrogen production process specifically comprises:
First alcohol and water in described liquid container is delivered to the interchanger heat exchange of hydrogen producer by raw material conveying device, enter 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 300 ℃～420 ℃;
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 350 ℃～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 0.15～5MPa to raw material, make the hydrogen that hydrogen producer makes have enough pressure; 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 0.7M 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%;
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.
Beneficial effect of the present invention is: the methanol-water hydrogen generating system that can start fast that the present invention proposes, and capable of fast starting, conventionally only need in 10 minutes; Meanwhile, it is methanol gasifying that hydrogen generating system only needs to make heating rod by electric energy, and seldom, common 2 batteries are enough (this hydrogen generating system can be used for mobile hydrogen making machine to consumed energy) just.Therefore of the present invention practical, coordinate hydrogen gas generation machine, can be for people's routine use.
In addition, by improving the transmitting power of raw material conveying device, make the hydrogen that hydrogen producer makes there is enough pressure, can improve hydrogen production efficiency and make the purity of hydrogen.
Accompanying drawing explanation
Fig. 1 is the composition schematic diagram of the present invention's methanol-water hydrogen generating system that can start fast.
Fig. 2 is the structural representation of the device for rapidly starting of hydrogen generating system of the present invention.
Fig. 3 is the structural representation of hydrogen producer and heating pipe line thereof.
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 methanol-water hydrogen generating system that can start fast, and described system comprises: liquid container 10, raw material conveying device 50, device for rapidly starting 40, hydrogen producer 20, membrane separation unit 30.
As shown in Figure 2, described device for rapidly starting 40 comprises housing 41, heating arrangements 42, gasification pipeline 43, and the internal diameter of gasification pipeline 43 is 1～2mm, and gasification pipeline 43 is wound on heating arrangements 42; Described heating arrangements can be electrically heated rod, utilizes alternating-current or store battery, drying battery.
One end of described gasification pipeline 43 connects liquid container 10, and methyl alcohol is sent in gasification pipeline 43; The other end of gasification pipeline 43 is exported vaporized methyl alcohol, then by ignition mechanism ignition; Or the other end of gasification pipeline 43 is exported vaporized methyl alcohol, and the methanol temperature of output reaches spontaneous ignition temperature, methyl alcohol directly spontaneous combustion from 43 outputs of gasification pipeline; Described device for rapidly starting 40 provides the startup energy for hydrogen producer (whole hydrogen generating system in other words).
Refer to Fig. 3, in order to improve the rate of heating 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 catalyzer (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 heating efficiency.
In addition, the second starter gear can also be set, described the second starter gear comprises the second gasification pipeline, and the main body of the second gasification pipeline is arranged at 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 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.Setting-up time after the second starter gear can continue to make the methyl alcohol of gasification, can close above-mentioned device for rapidly starting, thereby further reduces the dependence to extra powers such as electric energy.
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:
Heating arrangements energising setting-up time, mechanism to be heated reaches the backward gasification pipeline of design temperature and passes into methyl alcohol; Because gasification pipeline is closely wound on heating arrangements, methanol temperature progressively raises; Gasification pipeline is exported vaporized methyl alcohol, then by ignition mechanism ignition; Or gasification pipeline is exported vaporized methyl alcohol, and the methanol temperature of output reaches spontaneous ignition temperature, methyl alcohol directly spontaneous combustion from the output of gasification pipeline;
The methyl alcohol of gasification is by burning heat release, for hydrogen producer provides the startup energy; Described reformer chamber inwall is provided with heating pipe line, is placed with catalyzer 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.
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.
Embodiment bis-
The difference of the present embodiment and embodiment mono-is, in the present embodiment, methanol-water hydrogen generating system of the present invention comprises: liquid container, raw material conveying device, device for rapidly starting, hydrogen producer, membrane separation unit.
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 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; 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 300 ℃～420 ℃.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 350 ℃～570 ℃; In separate chamber, be provided with membrane separation apparatus, from the aerogenesis end of membrane separation apparatus, obtain hydrogen.By above-mentioned improvement, 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; Meanwhile, preheating method of the present invention (separate chamber being arranged to the top of reformer chamber) is very convenient.
In addition, 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.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 0.7M Pa.By this, improve, make the hydrogen that hydrogen producer makes there is enough pressure, can improve hydrogen production efficiency and make the purity of hydrogen.
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, thereby can reduce the dependence to extra power, and adaptive ability is strong.
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%.The present invention utilizes this palladium membrane separation unit, and the purity of hydrogen is higher.
The present invention discloses a kind of hydrogen production process of above-mentioned methanol-water hydrogen generating system simultaneously, 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:
Heating arrangements energising setting-up time, mechanism to be heated reaches the backward gasification pipeline of design temperature and passes into methyl alcohol; Because gasification pipeline is closely wound on heating arrangements, methanol temperature progressively raises; Gasification pipeline is exported vaporized methyl alcohol, then by ignition mechanism ignition; Or gasification pipeline is exported vaporized methyl alcohol, and the methanol temperature of output reaches spontaneous ignition temperature, methyl alcohol directly spontaneous combustion from the output of gasification pipeline;
The methyl alcohol of gasification is by burning heat release, for hydrogen producer provides the startup energy; Described reformer chamber inwall is provided with heating pipe line, is placed with catalyzer 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, close device for rapidly starting, the hydrogen partial being made by hydrogen producer is or/and residual air maintains hydrogen producer by burning moves.Hydrogen production process specifically comprises:
First alcohol and water in described liquid container is delivered to the interchanger heat exchange of hydrogen producer by raw material conveying device, enter 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 300 ℃～420 ℃.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 350 ℃～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 0.15～5MPa to raw material, make the hydrogen that hydrogen producer makes have enough pressure; 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 0.7M 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%.
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.
In sum, the methanol-water hydrogen generating system that can start fast that the present invention proposes, capable of fast starting, conventionally only need in 10 minutes; Meanwhile, it is methanol gasifying that hydrogen generating system only needs to make heating rod by electric energy, and seldom, common 2 batteries are enough (this hydrogen generating system can be used for mobile hydrogen making machine to consumed energy) just.Therefore of the present invention practical, coordinate hydrogen gas generation machine, can be for people's routine use.
In addition, by improving the transmitting power of raw material conveying device, make the hydrogen that hydrogen producer makes there is enough pressure, can improve hydrogen production efficiency and make the purity of hydrogen.
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 (10)
1. the methanol-water hydrogen generating system that can start fast, is characterized in that, described system comprises: liquid container, raw material conveying device, device for rapidly starting, hydrogen producer, membrane separation unit;
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 liquid container is connected with hydrogen producer; In liquid container, store liquid first alcohol and water;
Described system utilizes device for rapidly starting to provide the startup energy to start; Device for rapidly starting comprises heating arrangements, gasification pipeline, and the internal diameter of gasification pipeline is 1～2mm, and gasification pipeline is closely wound on heating arrangements; One end of described gasification pipeline connects liquid container, and methyl alcohol is sent in gasification pipeline; The other end of gasification pipeline is exported vaporized methyl alcohol, then by ignition mechanism ignition; Or the other end of gasification pipeline is exported vaporized methyl alcohol, and the methanol temperature of output reaches spontaneous ignition temperature, methyl alcohol directly spontaneous combustion from the output of gasification pipeline; Described device for rapidly starting provides the startup energy for hydrogen producer; Described reformer chamber inwall is provided with heating pipe line, is placed with catalyzer in heating pipe line; Described device for rapidly starting is that reformer chamber heats by heating described heating pipe line;
After described hydrogen generating system starts, the hydrogen that hydrogen generating system makes by hydrogen producer provides operation the required energy;
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 300 ℃～420 ℃;
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 350 ℃～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 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 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 0.7MPa;
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. the methanol-water hydrogen generating system that can start fast, is characterized in that, described system comprises: liquid container, raw material conveying device, device for rapidly starting, hydrogen producer, membrane separation unit;
Described device for rapidly starting comprises heating arrangements, gasification pipeline, and gasification pipeline is wound on heating arrangements;
One end of described gasification pipeline connects liquid container, and methyl alcohol is sent in gasification pipeline; The other end of gasification pipeline is exported vaporized methyl alcohol, then by ignition mechanism ignition; Or the other end of gasification pipeline is exported vaporized methyl alcohol, and the methanol temperature of output reaches spontaneous ignition temperature, methyl alcohol directly spontaneous combustion from the output of gasification pipeline; Described device for rapidly starting provides the startup energy for hydrogen producer.
3. the methanol-water hydrogen generating system that can start fast according to claim 2, is characterized in that:
Described hydrogen producer comprises reformer chamber, and reformer chamber inwall is provided with heating pipe line, is placed with catalyzer in heating pipe line; Described device for rapidly starting is that reformer chamber heats by heating described heating pipe line.
4. the methanol-water hydrogen generating system that can start fast according to claim 2, 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 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 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 0.7MPa.
5. the methanol-water hydrogen generating system that can start fast 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%.
6. the methanol-water hydrogen generating system that can start fast according to claim 2, is characterized in that:
Described heating arrangements is electrically heated rod.
7. a hydrogen production process for methanol-water hydrogen generating system described in claim 1, is characterized in that, described method comprises the steps:
Step S1, quick setting up procedure; Described hydrogen generating system utilizes device for rapidly starting to provide the startup energy to start; Specifically comprise:
Heating arrangements energising setting-up time, mechanism to be heated reaches the backward gasification pipeline of design temperature and passes into methyl alcohol; Because gasification pipeline is closely wound on heating arrangements, methanol temperature progressively raises; Gasification pipeline is exported vaporized methyl alcohol, then by ignition mechanism ignition; Or gasification pipeline is exported vaporized methyl alcohol, and the methanol temperature of output reaches spontaneous ignition temperature, methyl alcohol directly spontaneous combustion from the output of gasification pipeline;
The methyl alcohol of gasification is by burning heat release, for hydrogen producer provides the startup energy; Described reformer chamber inwall is provided with heating pipe line, is placed with catalyzer in heating pipe line; Described device for rapidly starting is that reformer chamber heats by heating described heating pipe line;
After step S2, system start, the hydrogen that hydrogen generating system makes by hydrogen producer provides operation the required energy; Treat that hydrogen generating system operation makes enough hydrogen, close device for rapidly starting, the hydrogen partial being made by hydrogen producer is or/and residual air maintains hydrogen producer by burning moves; Hydrogen production process specifically comprises:
First alcohol and water in described liquid container is delivered to the interchanger heat exchange of hydrogen producer by raw material conveying device, enter 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 300 ℃～420 ℃;
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 350 ℃～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 0.15～5MPa to raw material, make the hydrogen that hydrogen producer makes have enough pressure; 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 0.7MPa; 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%;
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.
8. a hydrogen production process for the described methanol-water hydrogen generating system of one of claim 2 to 6, is characterized in that, described method comprises the steps:
Step S1, quick setting up procedure; Described hydrogen generating system utilizes device for rapidly starting to provide the startup energy to start; Specifically comprise:
Gasification pipeline passes into methyl alcohol, and methyl alcohol is by heating arrangements heating and gasifying;
Gasification pipeline is exported vaporized methyl alcohol, then by ignition mechanism ignition; Or gasification pipeline is exported vaporized methyl alcohol, and the methanol temperature of output reaches spontaneous ignition temperature, methyl alcohol directly spontaneous combustion from the output of gasification pipeline;
Vaporized methyl alcohol is by burning heat release, for hydrogen producer provides the startup energy.
9. hydrogen production process according to claim 8, is characterized in that:
In described step S1, heating arrangements is electrically heated rod, energising setting-up time, and mechanism to be heated reaches the backward gasification pipeline of design temperature and passes into methyl alcohol; Because gasification pipeline is closely wound on heating arrangements, methanol temperature progressively raises, until gasification;
Described reformer chamber inwall is provided with heating pipe line, is placed with catalyzer in heating pipe line; Described device for rapidly starting is that reformer chamber heats by heating described heating pipe line.
10. hydrogen production process according to claim 8, is characterized in that:
Described hydrogen production process also comprises step S2: after 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; Hydrogen production process specifically comprises:
First alcohol and water in described liquid container is delivered to the interchanger heat exchange of hydrogen producer by raw material conveying device, enter 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 300 ℃～420 ℃;
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 350 ℃～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 0.15～5MPa to raw material, make the hydrogen that hydrogen producer makes have enough pressure; 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 0.7MPa; 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%;
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.
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| CN103940185A (en) * | 2014-04-10 | 2014-07-23 | 上海合既得动氢机器有限公司 | Methyl alcohol reforming electricity generation refrigerator system and control method |
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