CN104803351A - Hydrogen production device and process for hydrogen refueling station - Google Patents
Hydrogen production device and process for hydrogen refueling station Download PDFInfo
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- CN104803351A CN104803351A CN201510183020.1A CN201510183020A CN104803351A CN 104803351 A CN104803351 A CN 104803351A CN 201510183020 A CN201510183020 A CN 201510183020A CN 104803351 A CN104803351 A CN 104803351A
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Abstract
The invention discloses a hydrogen production device and process for a hydrogen refueling station. The hydrogen production device comprises a control device, a methanol water storing and conveying device and at least three sets of methanol water reforming and hydrogen manufacturing modules, wherein the control device is in electric connection with the methanol water storing and conveying device and all the methanol water reforming and hydrogen manufacturing modules to control the working stations of the methanol water storing and conveying device and all the methanol water reforming and hydrogen manufacturing modules; hydrogen manufactured by the methanol water reforming and hydrogen manufacturing modules is directly conveyed to a hydrogen filling system by a conveying pipeline; the control device controls a proper number of methanol water reforming and hydrogen manufacturing modules to work according to required hydrogen amount information of the hydrogen filling system. The hydrogen production device and process have the advantages that the modularization degree is high, single modules are small in size and quick in starting, a hydrogen storage tank is not needed, instant hydrogen manufacture and quick hydrogen separation can be realized, the stability is good, the intelligence degree is high, the parameters such as the hydrogen manufacturing temperature, the gas flowrate and the gas pressure can be controlled flexibly, the security is high and the reliability is strong.
Description
Technical field
The present invention relates to hydrogenation stations technical field, particularly a kind of hydrogen production plant of hydrogenation stations and technique.
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.
For the day by day universal environmental issue brought of reply orthodox car, international community reaches common understanding, and the alternative fuel of development environment close friend, walks Sustainable Development Road.The fuel cell car that hydrogen is fuel is used to be acknowledged as the most desirable, the most real, the most possible technology substituting orthodox car at present.Recent two decades comes, and national governments and Ge great energy company, motor corporation drop into huge fund one after another in the development and utilization of Hydrogen Energy, make fuel cell car technology obtain develop rapidly.Nearly ten years, for coordinating research and development, the demonstrating running of fuel cell car, more than 200 various types of hydrogenation stations has successively been built in the whole world, and these hydrogenation stations, except providing hydrogen for fuel cell car and annotating, are also various hydrogen-holder car filling hydrogen.
In the prior art, the hydrogen source of hydrogenation stations mainly contains water electrolysis hydrogen production mode, hydrogen making by natural gas reformation mode and other organic hydride hydrogen manufacturing mode.The patent of this respect has: 1, Chinese invention patent 200610088913.9 discloses a kind of hydrogen manufacturing hydrogen loading system and the method thereof that can fill hydrogen fast, and the hydrogen source of this hydrogen manufacturing hydrogen loading system is water electrolysis hydrogen production and hydrogen making by natural gas reformation; 2, Chinese invention patent application 201280050583.8 discloses a kind of hydrogenation stations, the hydrogen source of this hydrogenation stations is: utilize the hydride that the mass-produced hydrogen of refinery and aromatic hydrocarbons react and obtain, recycling transport trolley is transported to hydrogenation stations, finally hydride is obtained hydrogen through reforming reaction.But these class methods need to consume mineral fuel natively very in short supply, and this kind of hydrogen producer volume is large, startup is slow, intellectuality is low, poor stability, energy consumption are high.
Along with the progress of technology, methanol-water reforming hydrogen producing technology is developed gradually, and the hydrogen obtained by this reforming hydrogen producing technology is gradually by the hydrogen source as hydrogenation stations.Methanol-water reforming hydrogen producing technology is 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 1-5M Pa pressure condition under pass through catalyzer, 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.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.Methanol-water reforming hydrogen producing technology is utilized to obtain the hydrogen source of hydrogen as hydrogenation stations, be applied in the hydrogenation stations in the city such as Shanghai, Dalian at present, but, in existing hydrogenation stations, methanol-water reforming hydrogen producing technology all adopts single reformer, intelligent poor, cannot modularization, volume large, start slow, seriously, security is low in methanol feedstock waste, whole process need hydrogen-storage tank, hydrogen manufacturing and note stabilized hydrogen are difficult to ensure.
Summary of the invention
The technical problem to be solved in the present invention is for above-mentioned deficiency of the prior art, a kind of hydrogen production plant of hydrogenation stations is provided, this hydrogen production plant modularization is high, single module volume is little, startup is quick, need not hydrogen-storage tank, instant hydrogen manufacturing and sharp separation can go out hydrogen, good stability, intelligent high, the aspect state modulator such as hydrogen manufacturing temperature, gas flow and air pressure are sensitive, and security is high, reliability is strong.For this reason, the present invention also will provide a kind of production technique of hydrogen production plant of described hydrogenation stations.
For solving above-mentioned first technical problem, technical scheme of the present invention is:
A kind of hydrogen production plant of hydrogenation stations, comprise control device, methanol-water Storing and conveying device and at least three group methanol-water reformation hydrogen production modules, described control device and methanol-water Storing and conveying device and each organize methanol-water reformation hydrogen production module and be all electrically connected, to control the working order of methanol-water Storing and conveying device and each group methanol-water reformation hydrogen production module; The hydrogen that described each group of methanol-water reformation hydrogen production module obtains directly sends hydrogen loading system to by transport pipe, in the process that this hydrogen loading system is annotated at hydrogen, instant hydrogen demand amount is fed back to control device, this control device operates according to the methanol-water reformation hydrogen production module of the hydrogen demand amount information Control proper amt of hydrogen loading system, and controls the methanol-water reformation hydrogen production module conveying first alcohol and water raw material of methanol-water Storing and conveying device to running.
Described methanol-water Storing and conveying device comprises methanol-water storage vessel and transferpump, store liquid first alcohol and water raw material in described methanol-water storage vessel, described transferpump is used for the first alcohol and water feedstock transportation in methanol-water storage vessel to methanol-water reformation hydrogen production module; The quantity of described transferpump and the quantity of methanol-water reformation hydrogen production module match, and the quantity of described methanol-water storage vessel is equal to or less than the quantity of transferpump.
Described methanol-water reformation hydrogen production module comprises reformer, reformer chamber and hydrogen purification apparatus is provided with in this reformer, the temperature of reformer chamber is 300-570 DEG C of temperature, reformer chamber is provided with catalyzer, first alcohol and water is at the obtained hydrogen-containing gas of reformation hydrogen production reaction of reformer chamber generation first alcohol and water, 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 gas that heating exports from reformer chamber; Described connecting pipeline, as the buffering between reformer chamber and hydrogen purification apparatus, makes the temperature of the gas exported from reformer chamber identical with the temperature of hydrogen purification apparatus or close, obtains hydrogen, be supplied to hydrogen loading system from the aerogenesis end of hydrogen purification apparatus.
Described methanol-water reformation hydrogen production module comprises two kinds of preferred structure modes:
The preferred structure mode of the first methanol-water reformation hydrogen production module is: described methanol-water reformation hydrogen production module is integrated with interchanger, described interchanger is installed on the transport pipe between methanol-water Storing and conveying device and reformer, the first alcohol and water raw material of low temperature is in interchanger, the high-temperature gas exported with reformer chamber carries out heat exchange, and first alcohol and water material temperature raises, vaporization; Described reformer is provided with electric heater, and this electric heater provides 300-570 DEG C of temperature for reformer chamber; The hydrogen of the aerogenesis end output of described hydrogen purification apparatus, after interchanger, temperature reduces, then is supplied to hydrogen loading system.
Further, be also provided with compensation vapourizing unit between described interchanger and reformer, this compensation vapourizing unit is provided with electric heater, and described first alcohol and water raw material can be vaporized further after compensating vapourizing unit.
The preferred structure mode of the second methanol-water reformation hydrogen production module is: described methanol-water reformation hydrogen production module is integrated with interchanger, described interchanger is installed on the transport pipe between methanol-water Storing and conveying device and reformer, the first alcohol and water raw material of low temperature is in interchanger, the high-temperature gas exported with reformer chamber carries out heat exchange, and first alcohol and water material temperature raises, vaporization; Also vaporizing chamber is not had in described reformer, described first alcohol and water raw material enters vaporizing chamber vaporization in interchanger after heat exchange, methanol steam after vaporization and water vapor enter reformer chamber, and reformer chamber bottom and middle portion temperature are 300-420 DEG C, and the temperature on reformer chamber top is 400-570 DEG C; The all or part of top being arranged at reformer chamber of the connecting pipeline between described reformer chamber and hydrogen purification apparatus; The hydrogen of the aerogenesis end output of described hydrogen purification apparatus, after interchanger, temperature reduces, then is supplied to hydrogen loading system.
Further, described reformer one end is provided with starter gear, and this starter gear comprises cup, cup is provided with raw material input channel, heating and gasifying pipeline, portfire and temperature detection device; Described raw material input channel can input first alcohol and water raw material, and raw material input channel is connected with heating and gasifying pipeline, and first alcohol and water raw material enters after heating and gasifying pipeline through raw material input channel, exports from the end of heating and gasifying pipeline; The position of described portfire is corresponding with the end of heating and gasifying pipeline, for lighting a fire to the first alcohol and water raw material exported in heating and gasifying pipeline, first alcohol and water raw material is through ignition device afterfire, can heat heating and gasifying pipeline, make heating and gasifying ducted first alcohol and water material gasification and strengthen rapidly intensity of combustion, and then being reformer heating; Described temperature detection device is for detecting the other temperature of heating and gasifying pipeline; After described reformer starts hydrogen manufacturing, the hydrogen partial that reformer is obtained is or/and residual air is run by burning maintenance reformer.
Further again, described cup comprises the liquid containing portion above installation portion and installation portion, described raw material input channel, heating and gasifying pipeline, portfire and temperature detection device are all installed on the installation portion of cup, described liquid containing portion can hold the first alcohol and water raw material exported from heating and gasifying pipe end, and described liquid containing portion upper end is also provided with liquid Splashproof cover; Described heating and gasifying pipeline comprises straight-through pipeline section, pigtail and upper arch pipeline section successively, and described first alcohol and water raw material after straight-through pipeline section rises to extreme higher position, then can decline through pigtail spiral, then exports after upper arch pipeline section; The bottom side of described cup is provided with air intake cover plate, and this air intake cover plate is provided with air channel, and outside air can enter in reformer through this air channel; Described raw material input channel is provided with magnetic valve, opens or closes to control raw material input channel.
In technique scheme, described hydrogen purification apparatus is membrane separation unit, and this membrane separation unit is the membrane separation unit at porous ceramic surface Vacuum Deposition palladium-silver alloy, and coatings is palladium-silver alloy, the mass percent palladium of palladium-silver alloy accounts for 75%-78%, and silver accounts for 22%-25%.
For solving above-mentioned second technical problem, technical scheme of the present invention is:
A production technique for the hydrogen production plant of hydrogenation stations, comprises the following steps:
(1) hydrogen loading system is in hydrogen filling process, and instant hydrogen demand amount is fed back to control device;
(2) control device operates according to the methanol-water reformation hydrogen production module of instant hydrogen demand amount information Control proper amt, and controls the methanol-water reformation hydrogen production module conveying first alcohol and water raw material of methanol-water Storing and conveying device to running; When instant hydrogen demand amount is less, control less methanol-water reformation hydrogen production module running, when instant hydrogen demand amount is larger, control more methanol-water reformation hydrogen production module running;
(3) the work operational situation of each group methanol-water reformation hydrogen production module of control device detecting real-time, when any one group of methanol-water reformation hydrogen production module running is abnormal, the methanol-water reformation hydrogen production module that control device controls this exception shuts down, and control the methanol-water reformation hydrogen production module running that is in holding state, or the methanol-water reformation hydrogen production module controlled in other runnings accelerates hydrogen manufacturing speed, shut down with the methanol-water reformation hydrogen production module compensated because of this exception and the hydrogen manufacturing amount that reduces.
The invention has the beneficial effects as follows:
One, the present invention adopt at least three group methanol-water reformation hydrogen production modules, and the degree of modularity is high, and single methanol-water reformation hydrogen production modular volume is little, startup is quick, and the aspect state modulator such as hydrogen manufacturing temperature, gas flow and air pressure are sensitive;
The hydrogen that two, the present invention respectively organizes methanol-water reformation hydrogen production module obtained directly sends hydrogen loading system to by transport pipe, without the need to high pressure hydrogen storage containers such as hydrogen-storage tanks, the instant hydrogen manufacturing of energy and sharp separation go out hydrogen, thus eliminate hydrogen-storage tank cost, improve the degree of safety of hydrogen conveying, avoid the hydrogen leak even problem of hydrogen-storage tank blast that cause because hydrogen-storage tank is abnormal;
Three, due to the present invention, often to organize the hydrogen manufacturing amount of methanol-water reformation hydrogen production module much smaller relative to the hydrogen manufacturing amount of methanol-water reformation hydrogen production module single in prior art, such as, if the present invention arranges 100 groups of methanol-water reformation hydrogen production modules, the hydrogen manufacturing amount that so the present invention often organizes methanol-water reformation hydrogen production module only needs 1/100 of the hydrogen manufacturing amount of single methanol-water reformation hydrogen production module in prior art; When instant hydrogen demand amount is less, such as, when annotating the hydrogen of single fuel cell car, control device only needs to control less methanol-water reformation hydrogen production module (such as 10 groups) running; When instant hydrogen demand amount is larger, such as, when annotating the hydrogen of many fuel cell cars or hydrogen container car, control device then controls more methanol-water reformation hydrogen production module (such as 70 groups) running; Therefore, when the present invention adopts at least three group methanol-water reformation hydrogen production modules as hydrogen manufacturing agent set, greatly can reduce zero load, its overall power consumption is less, and first alcohol and water raw material consumption is lower, utilization ratio is high;
After four, the present invention adopts at least three group methanol-water reformation hydrogen production modules, when one group of methanol-water reformation hydrogen production module breaks down, other methanol-water reformation hydrogen production modules of hydrogen production plant can also run well, or the methanol-water reformation hydrogen production module replacement work being in holding state can be made, therefore, its stability and reliability is good, intelligent high, can prevent the great exception causing hydrogen loading system because of the paralysis of part methanol-water reformation hydrogen production module;
Five, the methanol-water reformation hydrogen production module noise of less hydrogen manufacturing amount is less, is conducive to reducing sound pollution;
Six, the present invention adopts at least three group methanol-water reformation hydrogen production modules, when methanol-water reformation hydrogen production module quantity is inadequate, methanol-water reformation hydrogen production module can be increased easily, improve hydrogen manufacturing amount, make methanol-water reformation hydrogen production module quantity of the present invention energy masterly ground resilient expansion;
After seven, the present invention arranges at least three group methanol-water reformation hydrogen production modules, the hydrogen delivery tube road that single methanol-water reformation hydrogen production module is sent to hydrogen loading system can be accomplished very little, the hydrogen delivery tube road of this very minor diameter significantly can improve its ability of bearing pressure, and (pipeline is less, bearing capacity is larger), thus significantly improve the safety performance of hydrogenation stations.
Accompanying drawing explanation
Fig. 1 is one-piece construction block diagram of the present invention.
Fig. 2 is the methanol-water Storing and conveying apparatus structure block diagram of one embodiment of the present invention.
Fig. 3 is the methanol-water Storing and conveying apparatus structure block diagram of another preferred embodiment of the present invention.
Fig. 4 is the methanol-water reformation hydrogen production modular structure block diagram of one embodiment of the present invention.
Fig. 5 is the methanol-water reformation hydrogen production modular structure block diagram of another preferred embodiment of the present invention.
Fig. 6 is the dispersed texture schematic diagram of reformer in Fig. 5.
Fig. 7 is the structural representation of reformer starter gear in Fig. 5.
Fig. 8 is the cup holder portion structural representation of reformer starter gear in Fig. 5.
Fig. 9 is the one-piece construction block diagram of the hydrogen loading system of hydrogenation stations.
Embodiment
Below in conjunction with accompanying drawing, structural principle of the present invention and principle of work are described in further detail.
As shown in Figure 9, for the one-piece construction skeleton diagram of the hydrogen loading system of hydrogenation stations, this hydrogen loading system comprises hydrogen booster apparatus 6, hydrogen filing provision 7 and with hydrogen storage equipment 8, wherein, hydrogen gas compressor is provided with in hydrogen booster apparatus 6, hydrogen filing provision 7 can arrange multiple stage, is fuel cell car or hydrogen container car with hydrogen storage equipment 8.The pressure of hydrogen produced from hydrogen production plant is 1.6Mpa ~ 4Mpa, after hydrogen booster apparatus 6, the pressure increase of hydrogen to 40Mpa ~ 75Mpa, and then inflates to fuel cell car or hydrogen container car etc. by hydrogen filing provision 7 with hydrogen storage equipment 8.
As shown in Figure 1, a kind of hydrogen production plant of hydrogenation stations, comprise control device 1, methanol-water Storing and conveying device 2 and at least three group methanol-water reformation hydrogen production modules 3, described control device 1 is organized methanol-water reformation hydrogen production module 3 with methanol-water Storing and conveying device 2 and each and is all electrically connected, to control the working order of methanol-water Storing and conveying device 2 and each group methanol-water reformation hydrogen production module 3; The hydrogen that described each group of methanol-water reformation hydrogen production module 3 obtains directly sends hydrogen loading system 4 to by transport pipe, in the process that this hydrogen loading system 4 is annotated at hydrogen, instant hydrogen demand amount is fed back to control device 1, this control device 1 operates according to the methanol-water reformation hydrogen production module 3 of the hydrogen demand amount information Control proper amt of hydrogen loading system 4, and control methanol-water Storing and conveying device 2 to running methanol-water reformation hydrogen production module 3 carry first alcohol and water raw material.In addition, the quantity of methanol-water reformation hydrogen production module 3 of the present invention is preferably 10 groups ~ 150 groups, and the hydrogen manufacturing speed of each methanol-water reformation hydrogen production module 3 is 1 ~ 10Nm
3/ h, is preferably 2 ~ 5Nm
3/ h; Further, the quantity of methanol-water reformation hydrogen production module 3 is preferably 50 groups ~ 100 groups, can better ensure the hydrogen demand amount of hydrogen loading system like this.
After the present invention arranges at least three group methanol-water reformation hydrogen production modules 3, the hydrogen delivery tube road that single methanol-water reformation hydrogen production module 3 is sent to hydrogen loading system can be accomplished very little, hydrogen delivery tube road of the present invention adopts diameter to be the stainless steel tube of 2 ~ 8mm, the hydrogen delivery tube road of this diameter significantly can improve its ability of bearing pressure, and (pipeline is less, bearing capacity is larger), thus significantly improve the safety performance of hydrogenation stations.Further, hydrogen delivery tube road is preferably and adopts diameter to be the stainless steel tube of 3 ~ 6mm.
As shown in Figures 2 and 3, described methanol-water Storing and conveying device 2 comprises methanol-water storage vessel 21 and transferpump 22, store liquid first alcohol and water raw material in described methanol-water storage vessel 21, described transferpump 22 for by the first alcohol and water feedstock transportation in methanol-water storage vessel 21 to methanol-water reformation hydrogen production module 3; The quantity of described transferpump 22 and the quantity of methanol-water reformation hydrogen production module 3 match, and the quantity of described methanol-water storage vessel 21 is equal to or less than the quantity of transferpump 22.In fig. 2, the quantity of methanol-water storage vessel 21 is independent 1, and the quantity of methanol-water storage vessel 21 and the quantity of transferpump 22 match in figure 3.
As shown in Figure 4 and Figure 5, described methanol-water reformation hydrogen production module 3 comprises reformer 31 or 32, reformer chamber 311 or 321 and hydrogen purification apparatus 312 or 322 is provided with in this reformer 31 or 32, the temperature of reformer chamber is 300-570 DEG C of temperature, reformer chamber is provided with catalyzer, in reformer chamber, methyl alcohol and water vapour pass through catalyzer under the pressure condition of 1-5M Pa, under the effect of catalyzer, there is the transformationreation of methanol decomposition reaction and carbon monoxide, generate hydrogen and carbonic acid gas, this is component more than, the gas solid catalytic reaction system of many reactions, 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, the H that reforming reaction generates
2and CO
2, 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 gas that heating exports from reformer chamber, described connecting pipeline, as the buffering between reformer chamber and hydrogen purification apparatus, makes the temperature of the gas exported from reformer chamber identical with the temperature of hydrogen purification apparatus or close, obtains hydrogen, be supplied to hydrogen loading system 4 from the aerogenesis end of hydrogen purification apparatus.The present invention respectively organizes the mode that methanol-water reformation hydrogen production module 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.
Described methanol-water reformation hydrogen production module 3 comprises two kinds of preferred structure modes:
As shown in Figure 4, the preferred structure mode of the first methanol-water reformation hydrogen production module 3 is: described methanol-water reformation hydrogen production module 3 is integrated with interchanger 33, described interchanger 33 is installed on the transport pipe between methanol-water Storing and conveying device 2 and reformer 31, the first alcohol and water raw material of low temperature is in interchanger 33, the high-temperature gas exported with reformer chamber 31 carries out heat exchange, and first alcohol and water material temperature raises, vaporization; Described reformer 31 is provided with electric heater 313, and this electric heater 313 provides 300-570 DEG C of temperature for reformer chamber 311; The hydrogen of the aerogenesis end output of described hydrogen purification apparatus 312, after interchanger 33, temperature reduces, then is supplied to hydrogen loading system 4.
Further, be also provided with between described interchanger 33 and reformer 31 and compensate vapourizing unit 34, this compensation vapourizing unit 34 is provided with electric heater 341, and described first alcohol and water raw material can be vaporized further after compensating vapourizing unit 34.
As shown in Figure 5, the preferred structure mode of the second methanol-water reformation hydrogen production module 3 is: described methanol-water reformation hydrogen production module 3 is integrated with interchanger 35, described interchanger 35 is installed on the transport pipe between methanol-water Storing and conveying device 2 and reformer 321, the first alcohol and water raw material of low temperature is in interchanger 35, the high-temperature gas exported with reformer chamber 321 carries out heat exchange, and first alcohol and water material temperature raises, vaporization; Vaporizing chamber (not shown) is not also had in described reformer 32, described first alcohol and water raw material enters vaporizing chamber vaporization in interchanger after 35 heat exchange, methanol steam after vaporization and water vapor enter reformer chamber 321, reformer chamber 321 bottom and middle portion temperature are 300-420 DEG C, and the temperature on reformer chamber 321 top is 400-570 DEG C; The all or part of top being arranged at reformer chamber of the connecting pipeline between described reformer chamber 321 and hydrogen purification apparatus 322; The hydrogen of the aerogenesis end output of described hydrogen purification apparatus 322, after interchanger 35, temperature reduces, then is supplied to hydrogen loading system 4.
Further, as shown in Figure 5-Figure 8, described reformer 32 one end is provided with starter gear 5, and this starter gear 5 comprises cup 51, cup 51 is provided with raw material input channel 52, heating and gasifying pipeline 53, portfire 54 and temperature detection device 55; Described raw material input channel 52 can input first alcohol and water raw material, and raw material input channel 52 is connected with heating and gasifying pipeline 53, and first alcohol and water raw material enters after heating and gasifying pipeline 53 through raw material input channel 52, exports from the end of heating and gasifying pipeline 53; The position of described portfire 54 is corresponding with the end of heating and gasifying pipeline 53, for lighting a fire to the first alcohol and water raw material exported in heating and gasifying pipeline 53, first alcohol and water raw material is through portfire 54 ignition, combustion, can heat heating and gasifying pipeline 53, make the first alcohol and water material gasification in heating and gasifying pipeline 53 and strengthen rapidly intensity of combustion, and then heating for reformer 32; Described temperature detection device 55 is for detecting the other temperature of heating and gasifying pipeline 53; After described reformer 32 starts hydrogen manufacturing, the hydrogen partial that reformer 32 is obtained is or/and residual air is run by burning maintenance reformer 32.Reformer 32 utilizes starter gear 5 to heat for reformer 32 just, just makes reformer 32 start, and then reforming reaction occurs, and start time can complete in 5 minutes, and very fast, after having started, starter gear 5 cuts out.
As Figure 6-Figure 8, described cup 51 comprises the liquid containing portion 512 above installation portion 511 and installation portion, described raw material input channel 52, heating and gasifying pipeline 53, portfire 54 and temperature detection device 55 are all installed on the installation portion 511 of cup, described liquid containing portion 512 can hold the first alcohol and water raw material exported from heating and gasifying pipeline 53 end, and described liquid containing portion 512 upper end is also provided with liquid Splashproof cover 513.After raw material input channel 52 inputs first alcohol and water raw material, when heating and gasifying pipeline 53 exports, unnecessary first alcohol and water raw material can be contained in the liquid containing portion 512 of cup, certainly, after first alcohol and water raw material burns rapidly, the first alcohol and water raw material in liquid containing portion 512 also can gasification, and combustion.Described liquid Splashproof cover 513 can prevent the first alcohol and water raw material splashes when gasification, and combustion in liquid containing portion 512.Described heating and gasifying pipeline 53 comprises straight-through pipeline section 531, pigtail 532 and upper arch pipeline section 533 successively, described first alcohol and water raw material can after straight-through pipeline section 531 rises to extreme higher position, decline through pigtail 532 spiral again, then export after upper arch pipeline section 533.Like this, when starter gear 5 is started working, first alcohol and water raw material enters heating and gasifying pipeline 53, and first alcohol and water raw material is under the effect of upper arch pipeline section 533, first alcohol and water raw material can ooze, so that portfire is lighted a fire from the end of upper arch pipeline section 533 in the mode of drippage; After lighting a fire successfully, because the entire length of pigtail 532 is long, heating surface area is large, and therefore, the first alcohol and water raw material in pigtail 532 can fully by thermal evaporation.
As Figure 6-Figure 8, the bottom side of described cup 51 is provided with air intake cover plate 56, this air intake cover plate is provided with air channel 561, outside air can enter in reformer 32 through this air channel, the outside air entered from this air channel 561 can be starter gear 5 provides oxygen, also can be reformer 32 and oxygen is provided, for improving air inlet, fan (not shown) can be increased outside air channel 561; Described raw material input channel 52 is provided with magnetic valve, opens or closes to control raw material input channel 52.Described portfire can adopt resistant to elevated temperatures lighter for ignition on market, such as polarity formula pulse type ignitor etc.
In technique scheme, described hydrogen purification apparatus 312 or 322 is membrane separation unit, and this membrane separation unit is the membrane separation unit at porous ceramic surface Vacuum Deposition palladium-silver alloy, and coatings is palladium-silver alloy, the mass percent palladium of palladium-silver alloy accounts for 75%-78%, and silver accounts for 22%-25%.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 production technique of the hydrogen production plant of hydrogenation stations, comprises the following steps:
(1), in the process that hydrogen loading system is annotated at hydrogen, instant hydrogen demand amount is fed back to control device;
(2) control device operates according to the methanol-water reformation hydrogen production module of instant hydrogen demand amount information Control proper amt, and controls the methanol-water reformation hydrogen production module conveying first alcohol and water raw material of methanol-water Storing and conveying device to running; When instant hydrogen demand amount is less, control less methanol-water reformation hydrogen production module running, when instant hydrogen demand amount is larger, control more methanol-water reformation hydrogen production module running;
(3) the work operational situation of each group methanol-water reformation hydrogen production module of control device detecting real-time, when any one group of methanol-water reformation hydrogen production module running is abnormal, the methanol-water reformation hydrogen production module that control device controls this exception shuts down, and control the methanol-water reformation hydrogen production module running that is in holding state, or the methanol-water reformation hydrogen production module controlled in other runnings accelerates hydrogen manufacturing speed, shut down with the methanol-water reformation hydrogen production module compensated because of this exception and the hydrogen manufacturing amount that reduces.
The above is only better embodiment of the present invention, every above embodiment is done according to technical scheme of the present invention any trickle amendment, equivalent variations and modification, all belong in the scope of technical solution of the present invention.
Claims (10)
1. the hydrogen production plant of a hydrogenation stations, it is characterized in that: comprise control device, methanol-water Storing and conveying device and at least three group methanol-water reformation hydrogen production modules, described control device and methanol-water Storing and conveying device and each organize methanol-water reformation hydrogen production module and be all electrically connected, to control the working order of methanol-water Storing and conveying device and each group methanol-water reformation hydrogen production module; The hydrogen that described each group of methanol-water reformation hydrogen production module obtains directly sends hydrogen loading system to by transport pipe, in the process that this hydrogen loading system is annotated at hydrogen, instant hydrogen demand amount is fed back to control device, this control device operates according to the methanol-water reformation hydrogen production module of the hydrogen demand amount information Control proper amt of hydrogen loading system, and controls the methanol-water reformation hydrogen production module conveying first alcohol and water raw material of methanol-water Storing and conveying device to running.
2. the hydrogen production plant of hydrogenation stations according to claim 1, it is characterized in that: described methanol-water Storing and conveying device comprises methanol-water storage vessel and transferpump, store liquid first alcohol and water raw material in described methanol-water storage vessel, described transferpump is used for the first alcohol and water feedstock transportation in methanol-water storage vessel to methanol-water reformation hydrogen production module; The quantity of described transferpump and the quantity of methanol-water reformation hydrogen production module match, and the quantity of described methanol-water storage vessel is equal to or less than the quantity of transferpump.
3. the hydrogen production plant of hydrogenation stations according to claim 1, it is characterized in that: described methanol-water reformation hydrogen production module comprises reformer, reformer chamber and hydrogen purification apparatus is provided with in this reformer, the temperature of reformer chamber is 300-570 DEG C of temperature, reformer chamber is provided with catalyzer, first alcohol and water is at the obtained hydrogen-containing gas of reformation hydrogen production reaction of reformer chamber generation first alcohol and water, reformer chamber is connected by connecting pipeline with hydrogen purification apparatus, the all or part of of connecting pipeline is arranged at reformer chamber, high temperature by reformer chamber continues the gas that heating exports from reformer chamber, described connecting pipeline, as the buffering between reformer chamber and hydrogen purification apparatus, makes the temperature of the gas exported from reformer chamber identical with the temperature of hydrogen purification apparatus or close, obtains hydrogen, be supplied to hydrogen loading system from the aerogenesis end of hydrogen purification apparatus.
4. the hydrogen production plant of hydrogenation stations according to claim 3, it is characterized in that: described methanol-water reformation hydrogen production module is integrated with interchanger, described interchanger is installed on the transport pipe between methanol-water Storing and conveying device and reformer, the first alcohol and water raw material of low temperature is in interchanger, the high-temperature gas exported with reformer chamber carries out heat exchange, and first alcohol and water material temperature raises, vaporization; Described reformer is provided with electric heater, and this electric heater provides 300-570 DEG C of temperature for reformer chamber; The hydrogen of the aerogenesis end output of described hydrogen purification apparatus, after interchanger, temperature reduces, then is supplied to hydrogen loading system.
5. the hydrogen production plant of hydrogenation stations according to claim 4, it is characterized in that: between described interchanger and reformer, be also provided with compensation vapourizing unit, this compensation vapourizing unit is provided with electric heater, and described first alcohol and water raw material can be vaporized further after compensating vapourizing unit.
6. the hydrogen production plant of hydrogenation stations according to claim 3, it is characterized in that: described methanol-water reformation hydrogen production module is integrated with interchanger, described interchanger is installed on the transport pipe between methanol-water Storing and conveying device and reformer, the first alcohol and water raw material of low temperature is in interchanger, the high-temperature gas exported with reformer chamber carries out heat exchange, and first alcohol and water material temperature raises, vaporization; Also vaporizing chamber is not had in described reformer, described first alcohol and water raw material enters vaporizing chamber vaporization in interchanger after heat exchange, methanol steam after vaporization and water vapor enter reformer chamber, and reformer chamber bottom and middle portion temperature are 300-420 DEG C, and the temperature on reformer chamber top is 400-570 DEG C; The all or part of top being arranged at reformer chamber of the connecting pipeline between described reformer chamber and hydrogen purification apparatus; The hydrogen of the aerogenesis end output of described hydrogen purification apparatus, after interchanger, temperature reduces, then is supplied to hydrogen loading system.
7. the hydrogen production plant of hydrogenation stations according to claim 6, it is characterized in that: described reformer one end is provided with starter gear, this starter gear comprises cup, cup is provided with raw material input channel, heating and gasifying pipeline, portfire and temperature detection device; Described raw material input channel can input first alcohol and water raw material, and raw material input channel is connected with heating and gasifying pipeline, and first alcohol and water raw material enters after heating and gasifying pipeline through raw material input channel, exports from the end of heating and gasifying pipeline; The position of described portfire is corresponding with the end of heating and gasifying pipeline, for lighting a fire to the first alcohol and water raw material exported in heating and gasifying pipeline, first alcohol and water raw material is through ignition device afterfire, can heat heating and gasifying pipeline, make heating and gasifying ducted first alcohol and water material gasification and strengthen rapidly intensity of combustion, and then being reformer heating; Described temperature detection device is for detecting the other temperature of heating and gasifying pipeline; After described reformer starts hydrogen manufacturing, the hydrogen partial that reformer is obtained is or/and residual air is run by burning maintenance reformer.
8. the hydrogen production plant of hydrogenation stations according to claim 7, it is characterized in that: described cup comprises the liquid containing portion above installation portion and installation portion, described raw material input channel, heating and gasifying pipeline, portfire and temperature detection device are all installed on the installation portion of cup, described liquid containing portion can hold the first alcohol and water raw material exported from heating and gasifying pipe end, and described liquid containing portion upper end is also provided with liquid Splashproof cover; Described heating and gasifying pipeline comprises straight-through pipeline section, pigtail and upper arch pipeline section successively, and described first alcohol and water raw material after straight-through pipeline section rises to extreme higher position, then can decline through pigtail spiral, then exports after upper arch pipeline section; The bottom side of described cup is provided with air intake cover plate, and this air intake cover plate is provided with air channel, and outside air can enter in reformer through this air channel; Described raw material input channel is provided with magnetic valve, opens or closes to control raw material input channel.
9. according to the hydrogen production plant of the hydrogenation stations in claim 3 ~ 8 described in any one, it is characterized in that: described hydrogen purification apparatus is membrane separation unit, this membrane separation unit is the membrane separation unit at porous ceramic surface Vacuum Deposition palladium-silver alloy, coatings is palladium-silver alloy, the mass percent palladium of palladium-silver alloy accounts for 75%-78%, and silver accounts for 22%-25%.
10. the production technique of the hydrogen production plant of the hydrogenation stations in claim 1 ~ 8 described in any one, is characterized in that, comprises the following steps:
(1) hydrogen loading system is in hydrogen filling process, and instant hydrogen demand amount is fed back to control device;
(2) control device operates according to the methanol-water reformation hydrogen production module of instant hydrogen demand amount information Control proper amt, and controls the methanol-water reformation hydrogen production module conveying first alcohol and water raw material of methanol-water Storing and conveying device to running; When instant hydrogen demand amount is less, control less methanol-water reformation hydrogen production module running, when instant hydrogen demand amount is larger, control more methanol-water reformation hydrogen production module running;
(3) the work operational situation of each group methanol-water reformation hydrogen production module of control device detecting real-time, when any one group of methanol-water reformation hydrogen production module running is abnormal, the methanol-water reformation hydrogen production module that control device controls this exception shuts down, and control the methanol-water reformation hydrogen production module running that is in holding state, or the methanol-water reformation hydrogen production module controlled in other runnings accelerates hydrogen manufacturing speed, shut down with the methanol-water reformation hydrogen production module compensated because of this exception and the hydrogen manufacturing amount that reduces.
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Application publication date: 20150729 |