CN205222680U - Methanol -water reformation hydrogen production system that zero carbon discharged and fuel cell car thereof - Google Patents
Methanol -water reformation hydrogen production system that zero carbon discharged and fuel cell car thereof Download PDFInfo
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- CN205222680U CN205222680U CN201520675721.2U CN201520675721U CN205222680U CN 205222680 U CN205222680 U CN 205222680U CN 201520675721 U CN201520675721 U CN 201520675721U CN 205222680 U CN205222680 U CN 205222680U
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The utility model discloses a methanol -water reformation hydrogen production system that zero carbon discharged and fuel cell car thereof, including methanol -water reservoir, delivery pump, first heat exchanger, reformer and carbon dioxide recovery unit, wherein: the reformer is equipped with reformation room, electromagnetic heater and hydrogen purification device, and electromagnetic heater provides heat energy for the reformation room, the reformation room is used for methyl alcohol and water emergence reformation hydrogen generation, makes carbon dioxide and hydrogen, and it becomes the high temperature mist with water vapor mixing fails to hydrogen purification device, purification after -separating output hydrogen, and it is gaseous to export carbon dioxide and unreacted water vapor mixing simultaneously, and it is defeated to carbon dioxide recovery unit behind first heat exchanger, carbon dioxide recovery unit is removable modularization carbon dioxide recovery unit for retrieve carbon dioxide and partial steam. The utility model discloses can retrieve CO2, not influence the environment, not have hydrogen production system self and hurt, be favorable to the popularization and the application in new forms of energy fields such as fuel cell car.
Description
Technical field
The utility model relates to hydrogen Preparation equipment technical field, particularly a kind of methanol-water hydrogen production system employing reforming technology of zero carbon emission and fuel cell car thereof.
Background technology
Hydrogen is one of the optimal energy of a kind of 21 century, and when the coal of identical weight of burning, gasoline and hydrogen, the energy that hydrogen produces is maximum, and the product of its burning is water, does not have lime-ash and waste gas, does not pollute the environment; And the mainly CO that coal and oil combustion generate
2and SO
2, Greenhouse effect and acid rain can be produced respectively.Coal and reserves are limited, and hydrogen is mainly stored in water, and after burning, unique product is also water, can produce hydrogen continuously, be finished never.The distribution of hydrogen is very extensive, and water is exactly large " warehouse " of hydrogen, wherein contains the hydrogen of 11%.There is the hydrogen of 1.5% earth Rio; All contain hydrogen in oil, coal, Sweet natural gas, animal and plant body etc.The main body of hydrogen exists with the form of compound water, and earth surface about 70% is covered for water, and very greatly, therefore can say, hydrogen is the energy of " inexhaustible, nexhaustible " to moisture storage capacity.If can by suitable method from preparing hydrogen, so hydrogen also will be the energy that a kind of price is quite cheap.
At present, the annual production of hydrogen is about 3,600 ten thousand tons in the world, and hydrogen production process mainly contains two kinds: one, most hydrogen produce from oil, coal and Sweet natural gas, and this method needs to consume mineral fuel natively very in short supply; Two, about have the hydrogen of 4% to be produce by the method for brine electrolysis, it is large that this method consumes electric energy, do not calculate very much.Along with the progress of technology, adopt the technology of first alcohol and water reformation hydrogen production to be gradually developed, it can reduce the energy consumption in Chemical Manufacture and reduce costs, and is expected to alternative electric energy and consumes king-sized electrolysis hydrogen producing process.Advanced methanol steam reforming technology is utilized to produce H
2with CO
2mixed gas, then through palladium membrane separation apparatus be separated, H can be obtained respectively
2and CO
2.
With reference to Chinese invention application 201310340475.0(applicant: Shanghai Hejide Dynamic Hydrogen Machine Co., Ltd.), which disclose a kind of Methanol water hydrogen production system, the reformer chamber of methyl alcohol and steam reformer, at 350-409 DEG C of temperature 1-5MPa pressure condition under pass through catalyzer, under the effect of catalyzer, the transformationreation of methanol decomposition reaction and carbon monoxide occurs, generates hydrogen and carbonic acid gas, this is the gas solid catalytic reaction system of component more than, many reactions.Reactional equation is as follows: (1) CH
3oH → CO+2H
2; (2) H
2o+CO → CO
2+ H
2; (3) CH
3oH+H
2o → CO
2+ 3H
2, the H that reforming reaction generates
2and CO
2, then the palladium membrane separation apparatus through separate chamber is by H
2and CO
2be separated, obtain high-purity hydrogen, carbonic acid gas and unreacted steam then directly discharge the external world.
But because carbonic acid gas is as main greenhouse gas, its Greenhouse effect caused affect the original balance of atmospheric sphere and biosphere, cause a series of problem be closely related with human habitat, threaten the existence of the mankind, therefore, above-mentioned Methanol water hydrogen production system directly discharges CO
2be unfavorable for environment protection.Further, due to CO
2can be used as again carbon resource to be developed, be with a wide range of applications in industry and each department of national economy, and the CO that above-mentioned Methanol water hydrogen production system is directly discharged
2the CO that normally purity is higher
2(major impurity is steam), therefore, so direct discharge is real belongs to the wasting of resources.In addition, the carbonic acid gas of directly discharging from Methanol water hydrogen production system has comparatively high temps (between 405-570 DEG C), easily affect hydrogen generating system each several part equipment operation, when particularly applying to the new energy fields such as fuel cell car when Methanol water hydrogen production system, fuel cell car also needs the chimney arranging discharge carbonic acid gas specially, and such pole is unfavorable for the promotion and application of fuel cell car.
Utility model content
The technical problems to be solved in the utility model is for above-mentioned deficiency of the prior art, and provide a kind of methanol-water hydrogen production system employing reforming technology of zero carbon emission, this hydrogen generating system can reclaim CO
2, do not affect environment, to hydrogen generating system self fanout free region, be conducive to the promotion and application of the new energy fields such as fuel cell car.For this reason, the utility model also will provide the application of the methanol-water hydrogen production system employing reforming technology of this zero carbon emission.
For solving above-mentioned first technical problem, the technical solution of the utility model is: a kind of methanol-water hydrogen production system employing reforming technology of zero carbon emission, comprises methanol-water storage vessel, transferpump, First Heat Exchanger, reformer and carbon dioxide recovering apparatus, wherein:
Methanol-water storage vessel, stores liquid first alcohol and water in it;
Transferpump, for being delivered to the reformer chamber of reformer by the first alcohol and water in methanol-water storage vessel;
First Heat Exchanger, be installed on the transport pipe between transferpump and reformer, the first alcohol and water of low temperature is in First Heat Exchanger, and the high temperature carbon dioxide exported with reformer and steam mixed gas carry out heat exchange, methyl alcohol and water temp raise, and carbonic acid gas and steam mixed gas temperature reduce;
Reformer, is provided with reformer chamber, electromagnetic heater and hydrogen purification apparatus, and described electromagnetic heater comprises solenoid and metal is subject to magnet, can produce high frequency magnetic field, metal is generated heat by magnet is subject to magnetic field induction, for reformer chamber provides heat energy after solenoid energising; Described reformer chamber is provided with catalyzer, and first alcohol and water obtains carbonic acid gas and hydrogen in the reformation hydrogen production reaction of reformer chamber generation first alcohol and water, and this carbonic acid gas, hydrogen and unreacted steam are mixed into high-temperature gas mixture body, transfer to hydrogen purification apparatus; Described reformer chamber is connected by connecting pipeline with hydrogen purification apparatus, and all or part of of connecting pipeline is arranged at reformer chamber, and the high temperature by reformer chamber continues the high-temperature gas mixture body that heating exports from reformer chamber; Described connecting pipeline, as the buffering between reformer chamber and hydrogen purification apparatus, makes the temperature of the high-temperature gas mixture body exported from reformer chamber identical with the temperature of hydrogen purification apparatus or close; After hydrogen purification apparatus is separated high-temperature gas mixture body, hydrogen is exported from the hydrogen output terminal of hydrogen purification apparatus, export carbonic acid gas and unreacted steam mixed gas from the residual air output terminal of hydrogen purification apparatus, this carbonic acid gas and unreacted steam mixed gas transfer to carbon dioxide recovering apparatus after First Heat Exchanger;
Carbon dioxide recovering apparatus, for reclaiming the carbonic acid gas and part steam that export from reformer, this carbon dioxide recovering apparatus is removable modularization carbon dioxide recovering apparatus.
As to further elaboration of the present utility model:
The methanol-water hydrogen production system employing reforming technology of described zero carbon emission also comprises gas revolution pipeline, this gas revolution pipeline is arranged between carbon dioxide recovering apparatus and the reformer chamber of reformer, this gas revolution pipeline is provided with sensor and magnetic valve, this sensor is for responding to the air pressure in carbon dioxide recovering apparatus, when air pressure reach or higher than safe atmospheric pressure value time, magnetic valve is opened, portion gas in carbon dioxide recovering apparatus is delivered to the reformer chamber of reformer through gas revolution pipeline, when air pressure is lower than safe atmospheric pressure value, closed electromagnetic valve, gas revolution closedown of pipeline.
The methanol-water hydrogen production system employing reforming technology of described zero carbon emission also comprises apparatus for recovering, and this apparatus for recovering is arranged between carbon dioxide recovering apparatus and First Heat Exchanger; Described carbonic acid gas and steam mixed gas are after First Heat Exchanger cooling, and most of steam flows into apparatus for recovering and stores.Further, be provided with water pipe between apparatus for recovering and methanol-water storage vessel, the water in this apparatus for recovering can input to methanol-water storage vessel through water pipe, so that as raw water recycle.
Described reformer comprises insulation shell, reformer chamber and hydrogen purification apparatus from outside to inside successively, and the solenoid of described electromagnetic heater is arranged between insulation shell and reformer chamber, and described metal is arranged at reformer chamber by magnet.Further, described metal is provided with single or multiple lift by magnet, and metal is tubular structure or reticulated structure by magnet.
The methanol-water hydrogen production system employing reforming technology of described zero carbon emission also comprises the second interchanger, gas diverter, fuel cell and alternating current-direct current power conversion device, described second interchanger is installed on the transport pipe between transferpump and reformer, and the second interchanger and First Heat Exchanger are arranged in parallel, the first alcohol and water of low temperature in the second heat exchanger, the high-temperature hydrogen exported with reformer carries out heat exchange, methyl alcohol and water temp raise, and hydrogen temperature reduces; Described gas diverter is for shunting the hydrogen exported from the second interchanger, and after gas diverter shunting, hydrogen partial enters fuel cell; The oxygen generation electrochemical reaction that described fuel cell is used in hydrogen and air produces electric energy; Produce electric energy through alternating current-direct current power conversion device conversion after, for the electromagnetic heater of described transferpump and reformer is powered.
For solving above-mentioned second technical problem, the technical solution of the utility model is: the fuel cell car applying the methanol-water hydrogen production system employing reforming technology of described zero carbon emission, comprise methanol-water storage vessel, transferpump, First Heat Exchanger, reformer, carbon dioxide recovering apparatus, the second interchanger, fuel cell, alternating current-direct current power conversion device and automobile motor, wherein:
Methanol-water storage vessel, stores liquid first alcohol and water in it;
Transferpump, for being delivered to the reformer chamber of reformer by the first alcohol and water in methanol-water storage vessel;
First Heat Exchanger, be installed on the transport pipe between transferpump and reformer, the first alcohol and water of low temperature is in First Heat Exchanger, and the high temperature carbon dioxide exported with reformer and steam mixed gas carry out heat exchange, methyl alcohol and water temp raise, and carbonic acid gas and steam mixed gas temperature reduce;
Reformer, is provided with reformer chamber, electromagnetic heater and hydrogen purification apparatus, and described electromagnetic heater comprises solenoid and metal is subject to magnet, can produce high frequency magnetic field, metal is generated heat by magnet is subject to magnetic field induction, for reformer chamber provides heat energy after solenoid energising; Described reformer chamber is provided with catalyzer, and first alcohol and water obtains carbonic acid gas and hydrogen in the reformation hydrogen production reaction of reformer chamber generation first alcohol and water, and this carbonic acid gas, hydrogen and unreacted steam are mixed into high-temperature gas mixture body, transfer to hydrogen purification apparatus; Described reformer chamber is connected by connecting pipeline with hydrogen purification apparatus, and all or part of of connecting pipeline is arranged at reformer chamber, and the high temperature by reformer chamber continues the high-temperature gas mixture body that heating exports from reformer chamber; Described connecting pipeline, as the buffering between reformer chamber and hydrogen purification apparatus, makes the temperature of the high-temperature gas mixture body exported from reformer chamber identical with the temperature of hydrogen purification apparatus or close; After hydrogen purification apparatus is separated high-temperature gas mixture body, hydrogen is exported from the hydrogen output terminal of hydrogen purification apparatus, carbonic acid gas and unreacted steam mixed gas is exported from the residual air output terminal of hydrogen purification apparatus, this carbonic acid gas and unreacted steam mixed gas transfer to carbon dioxide recovering apparatus after First Heat Exchanger, and this hydrogen transfers to fuel cell;
Carbon dioxide recovering apparatus, for reclaiming the carbonic acid gas and part steam that export from reformer, this carbon dioxide recovering apparatus is removable modularization carbon dioxide recovering apparatus;
Second interchanger, is installed on the transport pipe between transferpump and reformer, and the second interchanger and First Heat Exchanger are arranged in parallel, the first alcohol and water of low temperature in the second heat exchanger, the high-temperature hydrogen exported with reformer carries out heat exchange, and methyl alcohol and water temp raise, and hydrogen temperature reduces;
Fuel cell, produces electric energy for the oxygen generation electrochemical reaction in hydrogen and air; The electric energy produced, after the conversion of alternating current-direct current power conversion device, for automobile motor is powered, is also that the electromagnetic heater of transferpump and reformer is powered simultaneously.
Described fuel cell car also comprises buffer battery, and the charging end of described buffer battery connects AC/DC changeover switch, and this buffer battery can be automobile motor and powers.
The beneficial effects of the utility model are:
One, due to reformer of the present utility model be provided with into reformer chamber heating electromagnetic heater, therefore have the following advantages: reformer is without the need to arranging combustion chamber, air inlet fan, air intake passage and smokestack, be a reformer closed on the whole, high-temp waste gas can not be discharged, avoid thermal waste, avoid because high-temp waste gas affects hydrogen generating system each several part equipment operation, avoid because of the destruction problem of burning to reformer; Solenoid itself can not produce heat substantially, and thus the life-span is long, and without the need to maintenance, without safeguarding replacement cost, work-ing life, the later stage was substantially without maintenance cost up to more than 10 years; Can produce high frequency magnetic field after solenoid energising, metal is generated heat rapidly by magnet is subject to magnetic field induction, and for reformer chamber provides heat energy, the thermal hysteresis of this type of heating is less, and control device is easy to precisely control reformer temperature; Adopt the mode that metal generates heat rapidly by magnetic field induction by magnet, reformer toggle speed is very quick, and efficiency is very high, the experiment proved that, can be reduced to 10 seconds the start time of reformer; The thermo-efficiency of electromagnetic heater is very high, can utilize more than 95% of electric energy, and homogeneous heating;
Two, because the utility model is provided with carbon dioxide recovering apparatus, make the emission-free discharge of methanol-water hydrogen production system employing reforming technology, thus physical environment is not affected, and, due to recovery is the carbon dioxide tail gas that purity is higher, thus reclaim easily, can be used as carbon resource to be developed, be with a wide range of applications in industry and each department of national economy, particularly carbonic acid gas is the main raw material preparing methyl alcohol, and methyl alcohol is the main raw material of methanol-water hydrogen production system employing reforming technology, therefore, the recycle of raw material can be realized after carbon dioxide recovering apparatus is set;
Three, because carbon dioxide recovering apparatus is removable modularization carbon dioxide recovering apparatus, therefore, retrieving arrangement is changed very convenient, after previous carbon dioxide recovering apparatus reclaims full carbonic acid gas, replaces with a rear carbon dioxide recovering apparatus.
Four, when the utility model methanol-water hydrogen production system employing reforming technology is applied to fuel cell car, fuel cell car does not need the chimney arranging discharge carbonic acid gas specially, is conducive to the promotion and application of fuel cell car like this, accomplishes real zero release.
Accompanying drawing explanation
Fig. 1 is the one-piece construction skeleton diagram of the utility model embodiment one.
Fig. 2 is the one-piece construction skeleton diagram of the utility model embodiment two.
Fig. 3 is the one-piece construction skeleton diagram of the utility model embodiment three.
Fig. 4 is reformer of the present utility model and First Heat Exchanger external structure schematic diagram.
Fig. 5 is the cross-sectional TV structure schematic diagram of reformer of the utility model one preferred embodiment.
Fig. 6 is a kind of preferred structure schematic diagram that metal is subject to magnet.
Fig. 7 is the another kind of preferred structure schematic diagram that metal is subject to magnet.
Embodiment
Below in conjunction with accompanying drawing, structural principle of the present utility model and principle of work are described in further detail.
Embodiment one
As described in Figure 1, a kind of methanol-water hydrogen production system employing reforming technology of zero carbon emission, comprises methanol-water storage vessel 1, transferpump 2, First Heat Exchanger 3, reformer 4 and carbon dioxide recovering apparatus 5, wherein:
Methanol-water storage vessel 1, stores liquid first alcohol and water in it;
Transferpump 2, for being delivered to the reformer chamber 41 of reformer 4 by the first alcohol and water in methanol-water storage vessel 1;
First Heat Exchanger 3, be installed on the transport pipe between transferpump 2 and reformer 4, the first alcohol and water of low temperature is in First Heat Exchanger 3, the high temperature carbon dioxide exported with reformer 4 and steam mixed gas carry out heat exchange, methyl alcohol and water temp raise, and carbonic acid gas and steam mixed gas temperature reduce;
Reformer 4, be provided with reformer chamber 41, electromagnetic heater 42 and hydrogen purification apparatus 43, described electromagnetic heater 42 comprises solenoid 421 and metal is subject to magnet 422, solenoid 421 can produce high frequency magnetic field after being energized, metal is made generated heat by magnetic field induction by magnet 422, for reformer chamber 41 provides the heat energy of 350-570 DEG C of temperature, be preferably 350-409 DEG C; Catalyzer is provided with in described reformer chamber 41, methyl alcohol and water vapor are in reformer chamber 41, catalyzer is passed through under the pressure condition of 1-5MPa, under the effect of catalyzer, there is the transformationreation of methanol decomposition reaction and carbon monoxide, generate hydrogen and carbonic acid gas, this is the gas solid catalytic reaction system of component more than, many reactions, and reactional equation is: (1) CH
3oH → CO+2H
2, (2) H
2o+CO → CO
2+ H
2, (3) CH
3oH+H
2o → CO
2+ 3H
2, this carbonic acid gas, hydrogen and unreacted steam are mixed into high-temperature gas mixture body, transfer to hydrogen purification apparatus 43; Described reformer chamber 41 is connected by connecting pipeline with hydrogen purification apparatus 43, and all or part of of connecting pipeline is arranged in reformer chamber 41, continues the high-temperature gas mixture body of heating from reformer chamber 41 output by the high temperature in reformer chamber 41; Described connecting pipeline, as the buffering between reformer chamber 41 and hydrogen purification apparatus 43, makes the temperature of the high-temperature gas mixture body exported from reformer chamber 41 identical with the temperature of hydrogen purification apparatus 43 or close; After hydrogen purification apparatus 43 pairs of high-temperature gas mixture bodies are separated, hydrogen is exported from the hydrogen output terminal of hydrogen purification apparatus 43, export carbonic acid gas and unreacted steam mixed gas from the residual air output terminal of hydrogen purification apparatus 43, this carbonic acid gas and unreacted steam mixed gas transfer to carbon dioxide recovering apparatus 5 after First Heat Exchanger 3;
Carbon dioxide recovering apparatus 5, for reclaiming the carbonic acid gas and part steam that export from reformer 4, this carbon dioxide recovering apparatus 5 is removable modularization carbon dioxide recovering apparatus 5.
As described in Figure 1, the methanol-water hydrogen production system employing reforming technology of described zero carbon emission also comprises gas revolution pipeline 6, this gas revolution pipeline 6 is arranged between the reformer chamber 41 of carbon dioxide recovering apparatus 5 and reformer 4, this gas revolution pipeline 6 is provided with sensor 61 and magnetic valve 62, this sensor 61 is for responding to the air pressure in carbon dioxide recovering apparatus 5, when air pressure reach or higher than safe atmospheric pressure value time, magnetic valve 62 is opened, portion gas (carbonic acid gas and other minimum gas) in carbon dioxide recovering apparatus 5 is delivered to the reformer chamber 41 of reformer 4 through gas revolution pipeline 6, when air pressure is lower than safe atmospheric pressure value, magnetic valve 62 cuts out, gas revolution pipeline 6 is closed.
As described in Figure 1, the methanol-water hydrogen production system employing reforming technology of described zero carbon emission also comprises apparatus for recovering 7, and this apparatus for recovering 7 is arranged between carbon dioxide recovering apparatus 5 and First Heat Exchanger 3; Described carbonic acid gas and steam mixed gas are after First Heat Exchanger 3 is lowered the temperature, and most of steam flows into apparatus for recovering 7 and stores.Further, be provided with water pipe between apparatus for recovering 7 and methanol-water storage vessel 1, the water in this apparatus for recovering 7 can input to methanol-water storage vessel 1 through water pipe, so that as raw water recycle.
As shown in Figure 4 and Figure 5, described reformer 4 comprises insulation shell 44, reformer chamber 41 and hydrogen purification apparatus 43 from outside to inside successively, the solenoid 421 of described electromagnetic heater 42 is arranged between insulation shell 44 and reformer chamber 41, described metal is arranged in reformer chamber 41 by magnet 422, and this metal can be that irony or stainless steel are subject to magnet by magnet.Further, described metal is provided with single or multiple lift by magnet 422, and metal is tubular structure (with reference to Fig. 6) or reticulated structure (with reference to Fig. 7) by magnet 422.The outside of described reformer chamber 41 and inner side are also provided with vaporization coil pipe 45, and first alcohol and water first passed through vaporization coil pipe 45 before entering reformer chamber 41, so that methyl alcohol and water vapor.
Described hydrogen purification apparatus 43 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 difference of the inside and outside pressure of membrane separation unit is more than or equal to 1.1MPa.The manufacturing process of membrane separation unit can refer to the patent of invention 201210563913.5 that the applicant Shanghai Hejide Dynamic Hydrogen Machine Co., Ltd. applied on December 21st, 2012, membrane separation apparatus of methanol-water hydrogen producer and preparation method thereof.The utility model respectively organizes the mode that methanol-water reformation hydrogen production power generation module group adopts reformer reformation hydrogen production at the temperature of 300-570 DEG C and under catalyst action, its hydrogen manufacturing speed and efficiency high, methanol-water feedstock conversion efficiency and utilization ratio high, good stability; Because the temperature of hydrogen purification apparatus is identical with reformer chamber temperature or close, therefore, hydrogen purification efficiency can be significantly improved and reduce hydrogen purification difficulty, realizing fast film and be separated.
Embodiment two
Embodiment two increases fuel cell power generating system on the basis of embodiment one, makes methanol-water hydrogen production system employing reforming technology by the fuel cell power generation of self to maintain operation, such as, maintain the operation of electrical control gear, transferpump and electromagnetic heater.As shown in Figure 2, the methanol-water hydrogen production system employing reforming technology of described zero carbon emission also comprises the second interchanger 8, gas diverter 9, fuel cell 10 and alternating current-direct current power conversion device 11, described second interchanger 8 is installed on the transport pipe between transferpump 2 and reformer 4, and the second interchanger 8 is arranged in parallel with First Heat Exchanger 3, the first alcohol and water of low temperature is in the second interchanger 8, the high-temperature hydrogen exported with reformer 4 carries out heat exchange, and methyl alcohol and water temp raise, and hydrogen temperature reduces; Described gas diverter 9 is for shunting the hydrogen exported from the second interchanger 8, after gas diverter 9 is shunted, hydrogen partial enters fuel cell 10, certainly, the hydrogen partial entering fuel cell 6 only accounts for the sub-fraction (hydrogen of such as 20%) of the hydrogen that reformer exports, and most of hydrogen then collects or exports to other hydrogen and uses equipment (hydrogen of such as 80%); Described fuel cell 10 produces electric energy for the oxygen generation electrochemical reaction in hydrogen and air, the anode at fuel cell: 2H
2→ 4H
++ 4e
-, H
2split into two protons and two electronics, proton is through proton exchange membrane (PEM), and electronics, by positive plate, by external loading, and enters cathode bipolar plate, the negative electrode at fuel cell: O
2+ 4e
-+ 4H
+→ 2H
2o, proton, electronics and O
2recombine is to form H
2o; Produce electric energy through alternating current-direct current power conversion device conversion after, for the electromagnetic heater 42 of described transferpump 2 and reformer 4 is powered.Further, described alternating current-direct current power conversion device 11 flows to the electricity of electromagnetic heater 42 is the high-frequency high-voltage of 20-40KHZ.Described methanol-water hydrogen production system employing reforming technology is also provided with hydrogen storage bottle 12, and this hydrogen storage bottle 12 in reformer 4 start-up course, can be fuel cell 10 inputting hydrogen, fuel cell 10 is worked, and produces electric energy, for the electromagnetic heater 42 of transferpump 2 and reformer 4 is powered.
Embodiment three
As shown in Figure 3, apply the fuel cell car of the methanol-water hydrogen production system employing reforming technology of described zero carbon emission, comprise methanol-water storage vessel 1, transferpump 2, First Heat Exchanger 3, reformer 4, carbon dioxide recovering apparatus 5, second interchanger 8, fuel cell 10, alternating current-direct current power conversion device 11 and automobile motor 13, wherein:
Methanol-water storage vessel 1, stores liquid first alcohol and water in it;
Transferpump 2, for being delivered to the reformer chamber 41 of reformer 4 by the first alcohol and water in methanol-water storage vessel 1;
First Heat Exchanger 3, be installed on the transport pipe between transferpump 2 and reformer 4, the first alcohol and water of low temperature is in First Heat Exchanger 3, the high temperature carbon dioxide exported with reformer 4 and steam mixed gas carry out heat exchange, methyl alcohol and water temp raise, and carbonic acid gas and steam mixed gas temperature reduce;
Reformer 4, be provided with reformer chamber 41, electromagnetic heater 42 and hydrogen purification apparatus 43, described electromagnetic heater 42 comprises solenoid 421 and metal is subject to magnet 422, solenoid 421 can produce high frequency magnetic field after being energized, metal is made generated heat by magnetic field induction by magnet 422, for reformer chamber 41 provides the heat energy of 350-570 DEG C of temperature, be preferably 350-409 DEG C; Catalyzer is provided with in described reformer chamber 41, methyl alcohol and water vapor are in reformer chamber 41, catalyzer is passed through under the pressure condition of 1-5MPa, under the effect of catalyzer, there is the transformationreation of methanol decomposition reaction and carbon monoxide, generate hydrogen and carbonic acid gas, this is the gas solid catalytic reaction system of component more than, many reactions, and reactional equation is: (1) CH
3oH → CO+2H
2, (2) H
2o+CO → CO
2+ H
2, (3) CH
3oH+H
2o → CO
2+ 3H
2, this carbonic acid gas, hydrogen and unreacted steam are mixed into high-temperature gas mixture body, transfer to hydrogen purification apparatus 43; Described reformer chamber 41 is connected by connecting pipeline with hydrogen purification apparatus 43, and all or part of of connecting pipeline is arranged in reformer chamber 41, continues the high-temperature gas mixture body of heating from reformer chamber 41 output by the high temperature in reformer chamber 41; Described connecting pipeline, as the buffering between reformer chamber 41 and hydrogen purification apparatus 43, makes the temperature of the high-temperature gas mixture body exported from reformer chamber 41 identical with the temperature of hydrogen purification apparatus 43 or close; After hydrogen purification apparatus 43 pairs of high-temperature gas mixture bodies are separated, hydrogen is exported from the hydrogen output terminal of hydrogen purification apparatus 43, export carbonic acid gas and unreacted steam mixed gas from the residual air output terminal of hydrogen purification apparatus 43, this carbonic acid gas and unreacted steam mixed gas transfer to carbon dioxide recovering apparatus 5 after First Heat Exchanger 3; This hydrogen transfers to fuel cell 10;
Carbon dioxide recovering apparatus 5, for reclaiming the carbonic acid gas and part steam that export from reformer 4, this carbon dioxide recovering apparatus 5 is removable modularization carbon dioxide recovering apparatus 5;
Second interchanger 8, is installed on the transport pipe between transferpump 2 and reformer 4, and the second interchanger 8 is arranged in parallel with First Heat Exchanger 3, the first alcohol and water of low temperature is in the second interchanger 8, the high-temperature hydrogen exported with reformer 4 carries out heat exchange, and methyl alcohol and water temp raise, and hydrogen temperature reduces;
Fuel cell 10, produces electric energy for the oxygen generation electrochemical reaction in hydrogen and air, the anode at fuel cell: 2H
2→ 4H
++ 4e
-, H
2split into two protons and two electronics, proton is through proton exchange membrane (PEM), and electronics, by positive plate, by external loading, and enters cathode bipolar plate, the negative electrode at fuel cell: O
2+ 4e
-+ 4H
+→ 2H
2o, proton, electronics and O
2recombine is to form H
2o; The electric energy produced, after alternating current-direct current power conversion device 11 is changed, for automobile motor 13 is powered, is also that the electromagnetic heater 42 of transferpump 2 and reformer 4 is powered simultaneously;
As shown in Figure 3, described fuel cell car also comprises buffer battery 14, and the charging end of described buffer battery 14 connects AC/DC changeover switch 11, and this buffer battery 14 can be automobile motor 13 and powers.By using the control device of fuel cell car, according to the charging capacity of the load buffer store battery of automobile motor, the electricity that fuel cell is sent supply automobile motor and buffer battery.Specifically, such as when accelerate time etc., time automobile motor load is large, to automobile motor supply from fuel cell and buffering battery electricity, or slow down, braking time etc. in situation, a part for the electricity produced by fuel cell is buffer battery charging.In addition, the equipment such as this buffer battery is raw material conveying device when automobile starting, the electric heater of the electric heater of reformer, compensation vapourizing unit are powered, when after automobile starting, then buffer battery stops powering to the electric heater of raw material conveying device, reformer, the equipment such as electric heater that compensates vapourizing unit, and by fuel cell-powered.
Embodiment four
A hydrogen production process for the methanol-water hydrogen production system employing reforming technology of zero carbon emission, comprises the following steps:
A. control device controls the startup of methanol-water reformation hydrogen production machine, first alcohol and water in methanol-water storage vessel after First Heat Exchanger, is delivered to the reformer chamber of reformer, in First Heat Exchanger by transferpump, methyl alcohol and water temp raise, and carbonic acid gas and steam mixed gas temperature reduce;
B. control device controls the electromagnetic heater work of reformer, high frequency magnetic field is produced after the solenoid energising of electromagnetic heater, the metal of electromagnetic heater is generated heat by magnetic field induction by magnet, for reformer chamber provides 350-570 DEG C of temperature, in reformer chamber, the first alcohol and water of vaporization is under catalyst action, there is the reformation hydrogen production reaction of first alcohol and water, obtained carbonic acid gas and hydrogen, this carbonic acid gas, hydrogen and unreacted steam are mixed into high-temperature gas mixture body, transfer to hydrogen purification apparatus;
C. the hydrogen purification apparatus that high-temperature gas mixture body enters reformer through connecting pipeline is separated, after hydrogen purification apparatus is separated, hydrogen is exported from the hydrogen output terminal of hydrogen purification apparatus, export carbonic acid gas and unreacted steam mixed gas from the residual air output terminal of hydrogen purification apparatus, this carbonic acid gas and unreacted steam mixed gas transfer to carbon dioxide recovering apparatus after First Heat Exchanger;
D., after previous carbon dioxide recovering apparatus reclaims full carbonic acid gas, a rear carbon dioxide recovering apparatus is replaced with.
In the above-described embodiments, described carbon dioxide recovering apparatus can adopt chemical solvent absorption method to reclaim carbonic acid gas, chemical absorption method refers to utilize carbonic acid gas and absorption agent to carry out intermediate compound that chemical reaction forms a kind of weak connection, then heating rich carbonated absorption liquid makes carbonic acid gas parse, the method that simultaneously stability agent is regenerated.Conventional sorbent material ammoniacal liquor, hot alkaline solution, Monoethanolamine MEA BASF (MEA), diethanolamine (DEA), trolamine (TEA), diisopropanolamine (DIPA) (ADIP), methyldiethanolamine (MEDA) and diglycolamine etc.
Have in above-described embodiment, carbonic acid gas may be used for basic industry, sugar industry, carbonated beverage industry, can be used as protection gas etc. at welding field.Particularly carbonic acid gas is the main raw material preparing methyl alcohol, and methyl alcohol is the main raw material of methanol-water hydrogen production system employing reforming technology, therefore, can realize the recycle of raw material after arranging carbon dioxide recovering apparatus.
The above is only the utility model better embodiment, every above embodiment is done according to the technical solution of the utility model any trickle amendment, equivalent variations and modification, all belong in the scope of technical solutions of the utility model.
Claims (9)
1. a methanol-water hydrogen production system employing reforming technology for zero carbon emission, is characterized in that: comprise methanol-water storage vessel, transferpump, First Heat Exchanger, reformer and carbon dioxide recovering apparatus, wherein:
Methanol-water storage vessel, stores liquid first alcohol and water in it;
Transferpump, for being delivered to the reformer chamber of reformer by the first alcohol and water in methanol-water storage vessel;
First Heat Exchanger, be installed on the transport pipe between transferpump and reformer, the first alcohol and water of low temperature is in First Heat Exchanger, and the high temperature carbon dioxide exported with reformer and steam mixed gas carry out heat exchange, methyl alcohol and water temp raise, and carbonic acid gas and steam mixed gas temperature reduce;
Reformer, is provided with reformer chamber, electromagnetic heater and hydrogen purification apparatus, and described electromagnetic heater comprises solenoid and metal is subject to magnet, can produce high frequency magnetic field, metal is generated heat by magnet is subject to magnetic field induction, for reformer chamber provides heat energy after solenoid energising; Described reformer chamber is provided with catalyzer, and first alcohol and water obtains carbonic acid gas and hydrogen in the reformation hydrogen production reaction of reformer chamber generation first alcohol and water, and this carbonic acid gas, hydrogen and unreacted steam are mixed into high-temperature gas mixture body, transfer to hydrogen purification apparatus; Described reformer chamber is connected by connecting pipeline with hydrogen purification apparatus, and all or part of of connecting pipeline is arranged at reformer chamber, and the high temperature by reformer chamber continues the high-temperature gas mixture body that heating exports from reformer chamber; Described connecting pipeline, as the buffering between reformer chamber and hydrogen purification apparatus, makes the temperature of the high-temperature gas mixture body exported from reformer chamber identical with the temperature of hydrogen purification apparatus or close; After hydrogen purification apparatus is separated high-temperature gas mixture body, hydrogen is exported from the hydrogen output terminal of hydrogen purification apparatus, export carbonic acid gas and unreacted steam mixed gas from the residual air output terminal of hydrogen purification apparatus, this carbonic acid gas and unreacted steam mixed gas transfer to carbon dioxide recovering apparatus after First Heat Exchanger;
Carbon dioxide recovering apparatus, for reclaiming the carbonic acid gas and part steam that export from reformer, this carbon dioxide recovering apparatus is removable modularization carbon dioxide recovering apparatus.
2. the methanol-water hydrogen production system employing reforming technology of zero carbon emission according to claim 1, it is characterized in that: also comprise gas revolution pipeline, this gas revolution pipeline is arranged between carbon dioxide recovering apparatus and the reformer chamber of reformer, this gas revolution pipeline is provided with sensor and magnetic valve, this sensor is for responding to the air pressure in carbon dioxide recovering apparatus, when air pressure reach or higher than safe atmospheric pressure value time, magnetic valve is opened, portion gas in carbon dioxide recovering apparatus is delivered to the reformer chamber of reformer through gas revolution pipeline, when air pressure is lower than safe atmospheric pressure value, closed electromagnetic valve, gas revolution closedown of pipeline.
3. the methanol-water hydrogen production system employing reforming technology of zero carbon emission according to claim 1, is characterized in that: also comprise apparatus for recovering, and this apparatus for recovering is arranged between carbon dioxide recovering apparatus and First Heat Exchanger; Described carbonic acid gas and steam mixed gas are after First Heat Exchanger cooling, and most of steam flows into apparatus for recovering and stores.
4. the methanol-water hydrogen production system employing reforming technology of zero carbon emission according to claim 3, it is characterized in that: between described apparatus for recovering and methanol-water storage vessel, be provided with water pipe, water in this apparatus for recovering can input to methanol-water storage vessel through water pipe, so that as raw water recycle.
5. the methanol-water hydrogen production system employing reforming technology of zero carbon emission according to claim 1, it is characterized in that: described reformer comprises insulation shell, reformer chamber and hydrogen purification apparatus from outside to inside successively, the solenoid of described electromagnetic heater is arranged between insulation shell and reformer chamber, and described metal is arranged at reformer chamber by magnet.
6. the methanol-water hydrogen production system employing reforming technology of zero carbon emission according to claim 5, is characterized in that: described metal is provided with single or multiple lift by magnet, and metal is tubular structure or reticulated structure by magnet.
7. the methanol-water hydrogen production system employing reforming technology of zero carbon emission according to claim 1, it is characterized in that: also comprise the second interchanger, gas diverter, fuel cell and alternating current-direct current power conversion device, described second interchanger is installed on the transport pipe between transferpump and reformer, and the second interchanger and First Heat Exchanger are arranged in parallel, the first alcohol and water of low temperature in the second heat exchanger, the high-temperature hydrogen exported with reformer carries out heat exchange, and methyl alcohol and water temp raise, and hydrogen temperature reduces; Described gas diverter is for shunting the hydrogen exported from the second interchanger, and after gas diverter shunting, hydrogen partial enters fuel cell; The oxygen generation electrochemical reaction that described fuel cell is used in hydrogen and air produces electric energy; Produce electric energy through alternating current-direct current power conversion device conversion after, for the electromagnetic heater of described transferpump and reformer is powered.
8. application rights requires the fuel cell car of the methanol-water hydrogen production system employing reforming technology of zero carbon emission described in 1, it is characterized in that: comprise methanol-water storage vessel, transferpump, First Heat Exchanger, reformer, carbon dioxide recovering apparatus, the second interchanger, fuel cell, alternating current-direct current power conversion device and automobile motor, wherein:
Methanol-water storage vessel, stores liquid first alcohol and water in it;
Transferpump, for being delivered to the reformer chamber of reformer by the first alcohol and water in methanol-water storage vessel;
First Heat Exchanger, be installed on the transport pipe between transferpump and reformer, the first alcohol and water of low temperature is in First Heat Exchanger, and the high temperature carbon dioxide exported with reformer and steam mixed gas carry out heat exchange, methyl alcohol and water temp raise, and carbonic acid gas and steam mixed gas temperature reduce;
Reformer, is provided with reformer chamber, electromagnetic heater and hydrogen purification apparatus, and described electromagnetic heater comprises solenoid and metal is subject to magnet, can produce high frequency magnetic field, metal is generated heat by magnet is subject to magnetic field induction, for reformer chamber provides heat energy after solenoid energising; Described reformer chamber is provided with catalyzer, and first alcohol and water obtains carbonic acid gas and hydrogen in the reformation hydrogen production reaction of reformer chamber generation first alcohol and water, and this carbonic acid gas, hydrogen and unreacted steam are mixed into high-temperature gas mixture body, transfer to hydrogen purification apparatus; Described reformer chamber is connected by connecting pipeline with hydrogen purification apparatus, and all or part of of connecting pipeline is arranged at reformer chamber, and the high temperature by reformer chamber continues the high-temperature gas mixture body that heating exports from reformer chamber; Described connecting pipeline, as the buffering between reformer chamber and hydrogen purification apparatus, makes the temperature of the high-temperature gas mixture body exported from reformer chamber identical with the temperature of hydrogen purification apparatus or close; After hydrogen purification apparatus is separated high-temperature gas mixture body, hydrogen is exported from the hydrogen output terminal of hydrogen purification apparatus, carbonic acid gas and unreacted steam mixed gas is exported from the residual air output terminal of hydrogen purification apparatus, this carbonic acid gas and unreacted steam mixed gas transfer to carbon dioxide recovering apparatus after First Heat Exchanger, and this hydrogen transfers to fuel cell;
Carbon dioxide recovering apparatus, for reclaiming the carbonic acid gas and part steam that export from reformer, this carbon dioxide recovering apparatus is removable modularization carbon dioxide recovering apparatus;
Second interchanger, is installed on the transport pipe between transferpump and reformer, and the second interchanger and First Heat Exchanger are arranged in parallel, the first alcohol and water of low temperature in the second heat exchanger, the high-temperature hydrogen exported with reformer carries out heat exchange, and methyl alcohol and water temp raise, and hydrogen temperature reduces;
Fuel cell, produces electric energy for the oxygen generation electrochemical reaction in hydrogen and air; The electric energy produced, after the conversion of alternating current-direct current power conversion device, for automobile motor is powered, is also that the electromagnetic heater of transferpump and reformer is powered simultaneously.
9. fuel cell car according to claim 8, is characterized in that: also comprise buffer battery, and the charging end of described buffer battery connects AC/DC changeover switch, and this buffer battery can be automobile motor and powers.
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| CN201520675721.2U CN205222680U (en) | 2015-09-02 | 2015-09-02 | Methanol -water reformation hydrogen production system that zero carbon discharged and fuel cell car thereof |
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| CN110862067B (en) * | 2019-10-28 | 2023-08-18 | 中科院大连化学物理研究所张家港产业技术研究院有限公司 | Low-pressure hydrogen production system of methanol water hydrogenation station and working method thereof |
| CN111453698A (en) * | 2020-05-14 | 2020-07-28 | 广东能创科技有限公司 | Small-size hydrogenation station of methanol-water |
| CN114142061A (en) * | 2021-12-01 | 2022-03-04 | 上海船舶研究设计院（中国船舶工业集团公司第六0四研究院） | Shipboard hydrogen fuel preparation system and hydrogen production method thereof |
| CN114142061B (en) * | 2021-12-01 | 2024-03-08 | 上海船舶研究设计院（中国船舶工业集团公司第六0四研究院） | Shipboard hydrogen fuel preparation system and hydrogen production method thereof |
| CN115020768A (en) * | 2022-06-20 | 2022-09-06 | 中科氢焱零碳人居科技(苏州)有限公司 | Methanol hydrogen production fuel cell combined heat and power supply system |
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