CN102782921A - Apparatus for generating hydrogen from ammonia stored in solid materials and integration thereof into low temperature fuel cells - Google Patents
Apparatus for generating hydrogen from ammonia stored in solid materials and integration thereof into low temperature fuel cells Download PDFInfo
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- CN102782921A CN102782921A CN2011800116731A CN201180011673A CN102782921A CN 102782921 A CN102782921 A CN 102782921A CN 2011800116731 A CN2011800116731 A CN 2011800116731A CN 201180011673 A CN201180011673 A CN 201180011673A CN 102782921 A CN102782921 A CN 102782921A
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- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
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- C01B3/047—Decomposition of ammonia
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Abstract
An ammonia-based hydrogen generation reactor (110) comprises: an ammonia cracking chamber (1) with an ammonia cracking catalyst, an inner combustion chamber (2) with a combustion or oxidation catalyst being in thermal contact with the ammonia cracking chamber, an ammonia gas preheating chamber (3), and an outer jacket annulus (6) for recovery of heat from the combustion products exiting the combustion chamber (2), wherein the cracking chamber (1), the inner combustion chamber (2), the preheating chamber (3) and the heat recovery jacket annulus (6) are arranged concentrically. Further described is a system for generating hydrogen comprising at least one ammonia storage unit (119, 120, 400) which, when in operation, is combined with at least one hydrogen generation reactor (110), wherein, when in operation, the waste heat of the at least one hydrogen generation reactor (110) is transferred to at least one storage unit (119, 120, 400) being in operation. A power generating device further comprising a fuel cell, and a method for operating the system for generating hydrogen are also described.
Description
Technical field
The present invention relates to be stored in such as the ground of the ammonia high energy efficiency in the solid-state storage material of metal amino salt generation hydrogen, and relate to use low-temperature fuel cell generation electric power through cracking.
Background technology
Ammonia is the chemicals that serves many purposes and be widely used.A kind of concrete purposes is the fuel of battery of acting as a fuel.If if the carbon dioxide of sealing up for safekeeping during traditional processing technology to be produced or can use nuclear energy or as the regenerative resource synthetic ammonia of wind (see, for example, United States Patent(USP) No. US 2008/0248353; And people such as Chakraborty, Fuel Cell Bulletin, in October, 2009, both full contents all are incorporated herein with the mode of quoting), then ammonia can be zero carbon fuel.
In order to help fuel, need make it be cracked into hydrogen and nitrogen through reactor through making ammonia as low-temperature fuel cell.The ammonia cracking is the endothermic process according to following reaction needed 46KJ/mol ammonia:
NH
3→1.5H
2+0.5N
2ΔH
298=46KJ/mol?NH
3
At WO 2006/113451 A2, United States Patent(USP) No. US 6; 936,363 B2, United States Patent(USP) No. US 7,267; Propose among 779 B2 (its all the elements all are incorporated herein with the mode of quoting) to be used to produce hydrogen, to be used to the ammonia cracker of fuel cell fueling.
For great majority are used, and especially in automotive applications, it is breakneck with the form of fluid under pressure ammonia being stored in the container.
Comprise and add or be adsorbed on the security risk that storage procedures in the solid can be avoided anhydrous liquid ammonia.
It is desirable to the ammonia cracker that high energy efficiency ground operation as far as possible is used to produce hydrogen.
Summary of the invention
In first aspect of the present invention, relate to a kind of reactor 110 based on ammonia generation hydrogen, said reactor based on ammonia generation hydrogen comprises:
-have an ammonia cracking chamber 1 of ammonia Cracking catalyst,
-inner combustion chamber 2, said inner combustion chamber have combustion catalyst or the oxidation catalyst with the thermo-contact of ammonia cracking chamber,
-ammonia preheating chamber 3, and
-outer shield annular element 6, said outer shield annular element is used for reclaiming heat from the combustion product that leaves combustion chamber 2,
Wherein, the guard shield annular element 6 of cracking chamber 1, inner combustion chamber 2, preheating chamber 3 and recovery heat is according to this order arranged concentric, thereby cracking chamber 1 forms innermost chamber.
The reactor 110 that generates hydrogen can also comprise: heat is changed fin 10, and said heat is changed fin and extended to the cracking chamber 1 from the surface of combustion chamber 2; With flow distributing hole 5, said flow distributing hole can supply to cracking chamber 1 with ammonia equably through making ammonia flow through flow distributing hole 5.
In second aspect; The present invention relates to a kind of system that is used to generate hydrogen; Said system comprises at least one storage unit 119,120,400; Said storage unit holds and can discharge the ammonia and the solid-state ammonia storage material 7 of metal amino salt preferably through desorb, said solid-state ammonia storage material when operation and the reactor 110 of at least one generation hydrogen according to claim 1 combined, wherein; When operation, at least one waste heat that generates the reactor 110 of hydrogen is passed at least one storage unit 119,120,400 of operating.
First preferred embodiment of second aspect is a kind of system; Wherein, At least one storage unit 119,120 has the concentric pipe 8 of hollow; The concentric pipe of said hollow partly or extends through the unit with connecting, and in the running, one in the reactor 110 of said at least one generation hydrogen is inserted in the said unit.
In the system of first preferred embodiment, the solid-state ammonia storage material 7 in the storage unit 119,120 can be as the reactor 110 of the generation hydrogen of operating down at the temperature conditions that is higher than 300 ℃ and the heat-insulating part between the surrounding environment.
In addition; In the system of first preferred embodiment, storage unit 120 can have annular compartment 9 at the place, outside portion, and said annular compartment has fluid intake and fluid issuing; Said fluid intake and fluid issuing are used to provide heat with desorb ammonia as heat exchanger.
In the system of first preferred embodiment; As first previous paragraphs is said, randomly make amendment; When the reactor 110 of said generation hydrogen inserted, storage unit 119,120 can have the space 11 between the inwall of reactor 110 that generates hydrogen and storage unit 119,120.
The reactor 110 that generates hydrogen can be operated down at the temperature conditions that is higher than 300 ℃; Under these circumstances; Space 11 can change or space 11 is filled by the fluid that can change, so that control generates reactor 110 and storage unit 119, the heat transmission between 120 of hydrogen.
Any one among the above embodiment of the system of second aspect of the present invention can also comprise: start unit 170, said start unit assist heating to generate the combustion chamber 2 of the reactor 110 of hydrogen; With heat exchanger 160, said heat exchanger reclaims and is formed on heat that the evaporation steam in the combustion chamber 2 produced and mixing air and from the ammonia of storage unit 119,120, to be used to get into combustion chamber 2.
Any one system among the above embodiment of the system of second aspect of the present invention can comprise two modules; Each includes in said at least one storage unit 119,120 said two modules; Said storage unit has the concentric pipe 8 of hollow; The concentric pipe of said hollow partly or connect and to extend through the unit, when operation, said at least one reactor 110 that generates hydrogen is inserted in the said unit.
In second preferred embodiment of second aspect of the present invention, system comprises: at least two storage units 400; With as separate unit and by one of fine isolation reactor 110 that generates hydrogen; Reactor from said generation hydrogen; The heat that is produced in the combustion chamber 2 can be fed to via valve and be positioned at least two outside storage units 400 or can be supplied to heat exchange area; Said heat exchange area extends in the storage unit 400, and said valve is directed to operating at least two storage units 400 in order with combustion product.
In the above system of second preferred embodiment of second aspect of the present invention; The heat of combustion product can be sent to storage unit 400 via heat exchanger 160; The combustion product of said heat exchanger spontaneous combustion in the future chamber 2 and/or from the exchange heat of the crackate of cracking chamber 1 to circulating fluid, said circulating fluid is transported at least one at least two storage units 400 with a part of heat
The third aspect of the invention is the TRT 60,70 that comprises alkaline fuel cell 151 or Proton Exchange Membrane Fuel Cells 152; Said TRT is provided with the system that is used to generate hydrogen of first preferred embodiment of the absorber 153 that is used to absorb little ammonia and second aspect; In said system; Solid-state ammonia storage material 7 in the storage unit 119,120 is as the reactor 110 of the generation hydrogen of operating down at the temperature conditions that is higher than 300 ℃ and the heat-insulating part of surrounding environment; Wherein, Hydrogen from said system is fed into alkaline fuel cell 151 or supplies to absorber 153, and after absorber 153 absorbed little ammonia, said hydrogen was fed into Proton Exchange Membrane Fuel Cells 152.
The TRT of the third aspect of the invention can also comprise pump 180; When the desorption pressures from the solid-state storage material 7 in the storage unit 2 is lower than when overcoming the required stress level of the pressure drop that during ammonia flows through TRT 60,70, taken place, said pump strengthens ammonia flowing from storage unit 119,120 to the reactor 110 that generates hydrogen.
Others of the present invention are the TRTs 60,70 that comprise alkaline fuel cell 151 or Proton Exchange Membrane Fuel Cells 152, and said TRT is provided with: at least one absorber 153 that is used to absorb little ammonia; The system that is used to generate hydrogen with second preferred embodiment of second aspect of the present invention; Feed hydrogen gas to alkaline fuel cell 151 or absorber 153 from said system; And after at least one absorber 153 absorbs little ammonia, feed hydrogen gas to Proton Exchange Membrane Fuel Cells 152; And pump 180, said pump is lower than at the desorption pressures from the solid-state storage material 7 in the storage unit 2 and strengthens ammonia flowing from storage unit 400 to the reactor 110 that generates hydrogen when overcoming the required stress level of the pressure drop that during ammonia flows through TRT 60,70, taken place.
In aspect another; The present invention relates to a kind of method that is used to operate the system that is used to generate hydrogen; Said system comprises at least one storage unit 119,120,400; Said storage unit holds and can discharge the ammonia and the solid-state ammonia storage material 7 of metal amino salt preferably through desorb, wherein, comes the waste heat of the reactor (110) of self-generating hydrogen to be recovered and to use in whole or in part desorb is transported to storage unit 2 from the heat of the ammonia of ammonia storage material 7.
Said method can also comprise that the fuel cell cooling fluid with fuel cell is incorporated into the outer shield of storage unit 2 and after carrying out heat exchange with ammonia storage material 7, cooling fluid is returned through pipe.
Description of drawings
Fig. 1 shows the schematic diagram of embodiment of reactor of the generation hydrogen of the entrance and exit with the reactor in the embodiments of the invention;
Fig. 2 shows the schematic cross sectional views of the embodiment of the reactor that generates hydrogen.Arrow shows the possible flow direction in different chamber;
Fig. 3 shows the schematic diagram of storage unit, and in the system that is used for generating hydrogen according to the present invention, said storage unit can use with the reactor of the generation hydrogen of Fig. 1 or Fig. 2;
Fig. 4 shows the schematic diagram of the embodiment of the storage unit with outer ring spare, and in the system that is used for generating hydrogen according to the present invention, said storage unit can use with the reactor of the generation hydrogen of Fig. 1 or Fig. 2;
The perspective view of the reactor of generation hydrogen-storage unit system implementation example that Fig. 5 has shown diagram.The reactor of said generation hydrogen also also provides the device that is used to isolate the reactor that generates hydrogen as heater and said storage unit;
Fig. 6 shows and is used to comprise storage unit and the routine flow chart of the system implementation of the reactor that generates hydrogen;
Fig. 7 shows and is used to comprise that storage unit and the reactor that generates hydrogen are to be used for producing through alkaline fuel cell the flow chart of the system implementation example of electric power;
Fig. 8 shows the flow chart that is used for such system implementation example, and said system comprises storage unit, generates the reactor of hydrogen and purifies the absorber from the crackate of little ammonia, to be used for producing electric power through Proton Exchange Membrane Fuel Cells;
Fig. 9 shows the flow chart that is used for such system implementation example; Said system comprises that reactor and the continuous purification of generation hydrogen of storage unit, cracking ammonia is from two absorbers of the crackate of little ammonia, to be used for producing electric power through Proton Exchange Membrane Fuel Cells;
Figure 10 shows the flow chart that is used for such system, and said system comprises two groups of embodiment and two absorbers of the reactor assembly of storage unit-generation hydrogen, to be used for producing electric power continuously through Proton Exchange Membrane Fuel Cells;
Figure 11 shows flow chart, and the heat that said flow chart has schematically shown the reactor exhaust of the hydrogen of self-generating in the future is directly delivered to one or more ammonia storage units;
Figure 12 shows flow chart, and said flow chart has schematically shown heat in the reactor exhaust of the hydrogen of self-generating in the future and carried fluid via heat and be delivered to one or more ammonia storage units.The said heat that comes the reactor exhaust of self-generating hydrogen at first is passed to said heat and carries fluid, said heat carry fluid then with said heat transferred to said one or more storage units.
Embodiment
Embodiments of the invention are discussed and are shown details with the mode of example and just to explanation in this article, and be to have presented said details for the most useful and understandable description that principle of the present invention and notion aspect are provided.In this regard; Do not have to attempt describing CONSTRUCTED SPECIFICATION of the present invention in more detail with the level of detail more required for the present invention than basic comprehension, the description together with accompanying drawing how some forms of the present invention embody in practice is conspicuous for those of skill in the art.
The present invention is intended to: the ammonia cracker, and said ammonia cracker can be bonded with each other with user friendly mode and the unit that holds solid-state ammonia storage material; And the waste heat of waste heat through utilizing cracker and fuel cell discharges the energy efficiency that ammonia in the storage material improves system as thermal source.
As beginning was mentioned, the ammonia cracking was the endothermic process according to following reaction needed 46KJ/mol ammonia:
NH
3→1.5H
2+0.5N
2ΔH
298=46KJ/mol?NH
3
This is equilibrium-controlled reaction, needs to realize near changing high reaction temperature (550 ℃ to 750 ℃) fully.Therefore, need the heat of reaction when very high temperature, to be transmitted, so that realize maximum conversion.Can come transfer of heat through electric heating or through burning such as the fuel of hydrogen.Electric heating is not only expensive with regard to whole efficiency, and it does not comprise in system under the situation of battery and between the starting period, can not use.Therefore, preferably, supply heat through the suitable fuel of burn ammonia preferably or hydrogen.
The technology of effectively isolating extreme high-temperature always is full of challenge.Therefore,, need reclaim burner exhaust heat as much as possible, so that other technology of some in system provides heat in order to improve energy efficiency.
Based on operational efficiency, fuel cell also can produce the waste heat more than 40%.For low-temperature fuel cell (typically under about 80 ℃ condition, moving), when quite low temperature (for example, 80 ℃), produce heat, this is considered to tow taste heat.Therefore, utilize low temperature Proton Exchange Membrane Fuel Cells (PEMFCs), this heat is dissipated in the environment gradually.This dissipation process self indicate system effectiveness than lossy, in addition, dissipation process consumption is used for the electric power of fans in operation or air blast.
Metal amino salt is ammonia absorption and desorption (desorb) materials, and said ammonia absorption and desorption material can be with the solid-state medium for storing that acts on ammonia.The preferred metal amino salt of using in the present invention has formula M
a(NH
3)
nX
z, wherein, M be selected from alkalinous metal (such as; Li, Na, K or Cs), alkaline-earth metal (such as; Mg, Ca, Sr or Ba) and/or transition metal (such as, V, Cr, Mn, Fe, Co, Ni, Cu or Zn) or they combination (such as, NaAl, KAl, K
2Zn, CsCU or K2Fe) one or more cations; X is the one or more anion that are selected from fluoride ion, chloride ion, bromide ion, iodide ion, nitrate ion, thiocyanate ion, sulfate ion, molybdate ion and phosphate ion; A is the cation quantity in each molecules of salt; Z is the anion quantity in each molecules of salt; And n is 2 to 12, preferably 6 to 8 ligancy.
The metal amino salt that can use has in the present invention all carried out describing more fully to quote among WO 2006/012903 A2 that mode is incorporated herein and the WO 2006/081824 at its full content.Its full content with the US 2008/0248353 that quotes mode and be incorporated herein in, the solid metallic amide is described for desirable " hydrogen carrier " of vehicle and stationary power generation system, reason is its high hydrogen content and contained safety problem.For this reason, metal amino salt is preferred solid-state ammonia storage material among the present invention.
From the solid-state ammonia storage material of for example metal amino salt, slough the arts demand heat of gas, see WO 1999/01205 A1, US 5,161,389 with WO 2006/012903 A2, its full content all is incorporated herein with the mode of quoting.There is diverse ways heat to be provided: can or heating element be placed on inside (US, 5,161,389 with WO 2006/012903 A2) through external heat hold-up vessel (WO 1999/01205 A1) and come transfer of heat to storage material.Yet, in order to improve system effectiveness, it is desirable to, design cracker and ammonia storage material with the mode of the total amount of heat of reduction system consume.
What is interesting is, can find such metal amino salt (Sr (NH for example
3)
8Cl
2Or Ca (NH
3)
8Cl
2), this metal amino salt discharges the ammonia that the overwhelming majority is stored in the temperature range that waste heat had of Proton Exchange Membrane Fuel Cells (PCMFCs).Therefore, the unique opportunity of fuel cell waste heat with further raising overall system efficiency also used in existence.
Therefore; The present invention relates to ammonia is carried out the high energy efficiency cracking; So that use the ammonia hydrogen producing in next life that is stored as solid-state ammonia storage material (being preferably metal amino salt); And relate to and make this system and low-temperature fuel cell (for example Proton Exchange Membrane Fuel Cells or alkaline fuel cell) form an integral body, to be used for efficient power generation.
In first aspect of the present invention, relate to and a kind ofly generate the reactor (after this being also referred to as " ammonia cracker " or " guard shield-cracker " or abbreviating " cracker " as) of hydrogen based on ammonia, the said reactor that generates hydrogen based on ammonia comprises and is used for ammonia and/or from combustion chamber, cracking chamber, ammonia preheating chamber and the burning gases heat? recovery chamber of the waste gas of anode of fuel cell.These four chambers of all of cracker are all concentric with the combustion chamber that is positioned at the middle part.Cracking chamber surrounds the combustion chamber.
Cracker can also comprise the sheet metal of a plurality of axial connections, and the heat of the device of spontaneous combustion in the future is dissipated to the cracking conduit to be used for better.Ammonia gets at the place, an end of preheating chamber, and after advancing through the length of preheating chamber, usually gets into cracking chamber through a plurality of entering hole that is arranged in the cracking chamber end cap.The combustion chamber can extend through the end cap of cracking chamber, so that the guiding burnt gas passes through guard shield.Cracking chamber holds that ammonia Cracking catalyst and combustion chamber hold can burnt ammonia or the combustion catalyst of hydrogen.
In another aspect; The present invention relates to a kind of system that is used to generate hydrogen; Said system comprises at least one storage unit 119,120,400, and said storage unit holds the solid-state ammonia storage material 7 (being preferably metal amino salt) that can discharge ammonia through desorb, in operation; The reactor 110 of the generation hydrogen of this system and first aspect is combined; Wherein, in operation, the heat energy of the heat of the combustion product of the hydrogen of the combustion chamber 2 of the reactor 110 of recovery self-generating hydrogen is passed at least one storage unit 119,120,400 of operating.
In a preferred embodiment; The system that is used to generate hydrogen can comprise storage unit (tube); Said storage unit holds for example metal amino salt; When system operation, guard shield-cracker can be tucked in the storage unit, and guard shield-cracker is tucked in the said storage unit or engages with said storage unit.
Hollow concentric pipe in the middle part of tube can extend connect tube or can be only from an end or sidepiece extend to the tube and do not connect said tube.
Tube can comprise hollow chamber, and for example with following guard shield form, all or part of outer surface that covers tube of said guard shield is to be used for reclaiming heat from the fuel cell cooling fluid.Can set up ammonia mentioned and from the fluid boundary of the cooling fluid of fuel cell as following.
The ammonia that is discharged by storage unit can be fed to cracker through pipe, and said pipe is via connecting cracker and storage unit as connecting fast or similarly engaging, to be convenient to change storage unit.
The invention still further relates to a kind of being used for reclaims heat and uses said heat to transmit the method for the heat of desorb ammonia whole or in part from guard shield-cracker.
The salt that is used to store ammonia have low-down conductive coefficient (can with
Many micropores high temperature insulating material is compared, and is approximately 10
-2W/mK).Utilize this character of salt, with the insulator of salt deposit as the cracker of under very high temperature, working.The device that is used for implementing said method comprises the metal amino salt block of cylindrical or similar 3D shape at container, and said container has the concentric pipe of hollow, and the concentric pipe of said hollow is extended and connected container.The diameter of hollow pipeline is at least enough wide, to admit cracker.
Said method can also comprise that the ammonia that will discharge from storage unit through pipe is incorporated into cracker, and said pipe connects cracker and storage unit via quick connection joining part or similar junction surface, to be convenient to change storage unit.
The invention still further relates to and a kind ofly be used to reclaim the heat of guard shield-cracker loss and use said heat via all or part of transmission desorb of annular space of the outer surface that surrounds hold-up vessel heat, to be used for from the fuel cell coolant recovery waste heat from the ammonia of ammonia storage material.
Said method can also comprise through pipe the fuel cell cooling fluid is incorporated into the outer shield of storage unit, and said pipe can be connected to outer shield via quick connection, and cooling fluid returned carrying out heat exchange (for example through managing) with storage material.
The description of embodiment
Hereinafter, with describing guard shield-cracker and storage unit and they in detail based on the application in the electricity generation system of solid-state ammonia.
Fig. 1 is the sketch map of guard shield-cracker 110.Ammonia and/or hydrogen (not shown in figure 1) are mixed with air mutually and mist gets into combustion chamber 2, and said combustion chamber is connected to the burning and gas-exhausting device, and is as shown in Figure 1.Hydrogen can be from the tail gas of anode of fuel cell.The ammonia that is used for cracking gets into reactor 110 through preheating chamber 3.
Fig. 2 illustrates ammonia flow dispensing orifice 5, and through said ammonia flow dispensing orifice, the ammonia of process preheating enters into cracking chamber 1.What illustrate equally is that heat is changed fin 10, and said heat is changed fin and is attached to the outer wall of combustion chamber 2 and extends in the cracking chamber 1, so that carry out heat distribution better, to be used for the heat absorption cracking of ammonia.The waste gas of combustion chamber 2 passed through outermost annular element 6 leave guard shield-cracker 110 through one or more outlets before.Cracking chamber waste gas leaves cracking chamber 1 through one or more outlets, and said cracking chamber waste gas is based on the operating position of guard shield-cracker and has the H of variable concentrations
2, N
2And NH
3Mixture.All imports of guard shield-cracker all are positioned at the place, same end of guard shield-cracker with outlet, thereby guarantee that counter-current gas flows in each chamber.The combustion chamber can hold any ammonia combustion catalyst or oxidation catalyst, for example 0.5% platinum on the 3mm of Johnson Matthey alumina pellet.Cracking chamber can hold any ammonia Cracking catalyst, for example 2% ruthenium on can the 3mm alumina pellet of the commercial Johnson Matthey that obtains.
Ammonia storage unit 119,120 is described now.As shown in Figure 3, storage unit 119 comprises cylinder, and said cylinder has the hollow concentric pipe 8 that connects the unit.8 diameter is enough big, so that insert guard shield-cracker 110.The ammonia that in space 7, comprises metal amino salt surrounds pipeline 8.Similar container 120 has been shown in Fig. 4, and wherein difference is that said container has annular space 9, and said annular space surrounds the main storeroom that holds metal amino salt 7.
Fig. 5 shows cracker and how can engage with storage unit 119 or 120.Can adjust space or gap 11 between the inwall of cracker 110 and storage unit 119,120, so that heat transmission and and then the control or influence the desorption efficiency of ammonia of control from the cracker to the storage unit.Insulation or conductive material can also be used for packing space, so that correspondingly reduce or increase the heat transmission from the cracker to the storage unit.
Fig. 6 shows the exemplary mobile device 50 based on solid-state ammonia generation hydrogen, and said equipment comprises ammonia storage unit 120, cracker 110, heat exchanger 160, start unit 170, vacuum pump 180 and battery (not shown).Cracker 110 is tucked in the storage unit 120.Only during first few minutes, need start unit 170, so that make combustion chamber 2 be ready to the ammonia that burns.As far as we know, there is not the catalyst of the ammonia that burns at ambient temperature, thus the catalyst bed in the combustion chamber 2 of needs heating cracker 110, to be used to the ammonia that burns.Start unit 170 comprises the heating rod that is inserted in the catalyst bed of being filled by the ammonia Cracking catalyst.When being supplied to ammonia, this unit produces H
2, N
2And NH
3Mixture, said mixture through manage 260 transport and with mix mutually through managing 220 air introduced.The air pump (not shown) can be used in and transports air.Between the starting period, vacuum pump 180 from storage unit 120 sucking-off ammonia, in said at, has not reached the suitable desorption pressures on atmospheric pressure when temperature reaches a level.Force mixture to enter into the combustion chamber 2 of cracker 110 then through heat exchanger 160, at said heat exchanger place, said mixture through with through manage 230 flow to heat exchanger 160 burner flue gas carry out heat exchange and by preheating.Heat exchanger 160 is mainly used in the fuel/air mixture that the evaporation heat of the steam that leaves combustion chamber 2 (steam) is delivered to entering.The pipeline of heat exchanger 160 is also with the mixing chamber that acts on air and combustion fuel.Burnt gas leaves heat exchanger 160 through managing 297.In case combustion chamber 2 is ready to the ammonia that burns, then connect ammonia stream from storage unit 120 through pipe 210, so that and air mixed, and then through heat exchanger 160 arrival combustion chambers 2.Cracking chamber 1 in the cracker 110 is heated to the required temperature of cracking, said cracking chamber and combustion chamber 2 thermo-contacts.According to required H
2Purity (according to escape ammonia (slip ammonia) concentration) can be selected temperature, but common said temperature is between 300 ℃ to 700 ℃.The ammonia that is used for cracking gets into cracking chamber 1 through pipe 200.In case heating cracking chamber 110 then is delivered to the storage unit 120 around being positioned at waste heat, so that be provided for the heat of desorb ammonia.Crackate (H
2, N
2And NH
3Mixture) leave cracker 110 through efferent duct 240.N if desired
2With the pure H that does not have ammonia
2, then can alternatively the palladium film be assembled in the gas exhaust piping.
In another embodiment of the present invention, used generator 60 with alkaline fuel cell 151.Equipment 60 shown in Fig. 7 has used the system 50 with the identical generation hydrogen shown in Fig. 6.In order to utilize the waste heat of fuel cell 151, the fuel battery cooling fluid is via the outer chamber 9 of pipe 270 through storage unit 120, to be used for exchange heat to storage material 7.The outlet of storage unit 120 need be discharged at cooling agent under the situation of more heats and can perhaps be walked around radiator via pipe 290 and directly arrive fuel cell via pipe 280 through radiator.The tail gas that comprises the anode of fuel cell of unconverted hydrogen can be sent to the combustion chamber 2 of cracker 110 via pipe 300, so that the hydrogen in the combustion flow.
An alternative embodiment of the invention is the generator 70 with PEM (PEM) fuel cell 152, will explain said generator now.Fig. 8 shows the unit affinity that equipment 70 and said equipment and Fig. 7 are described; Wherein, difference is that the waste gas from cracker 110 in the pipeline 240 passed through little ammonia absorber 153 before the anode side that is fed into Proton Exchange Membrane Fuel Cells 152.The reason that need do like this is that if in the anode aliment, deposit the ammonia of several ppm then the performance of Proton Exchange Membrane Fuel Cells 152 has irreversible degeneration tendency.Absorber 153 can be to be absorbed the cylindrical tube that material is filled.By acid (sulfuric acid (H for example
2SO
4)) activated carbon handled is as the good absorption material of ammonia.The y-type zeolite of some metal ion exchanged also can be used as absorbing material.Absorber can situ regeneration perhaps can be replaced with storage unit 120 through heating said absorber under the air-flow effect.As shown in Figure 9, also can use parallel at least two absorbers 153, to avoid that generator 70 is shut down.Use is to make to absorb to handle running continuously more than the purpose of one absorber 153: at least one absorber 153 will be in operation mode, and another absorber will be in regeneration mode.When if absorber 153 holds as the y-type zeolite of the Copper Ion Exchange of absorbent, then when air is through bed, just can accomplish situ regeneration through bed being heated to 200 ℃.This heat can by one in the thermal source of the energy in the system (as, the burning aerogenesis) provide.
Another embodiment of the present invention is continuous hydrogen maker, describes said continuous hydrogen maker now.Embodiment shown in Figure 10 comprises two storage units 120 of cracker unit 1 with embedding (being depicted as unit 1 and unit 2), two heat exchangers 160 and start units (SU) 170.Between the starting period, can 1 hold-up vessel 119,120 be pumped into the warm start unit from the unit with ammonia.Gas from the generation of start unit 170 (is generally 35%H
2And 11%N
2And remaining NH
3) with air mixed and the combustion chamber 2 through heat exchanger 160 arrival unit 1.In heat exchanger 160, carry out heat exchange from waste gas in the combustion chamber 2 and the input gas that enters into combustion chamber 2.In case combustion chamber 2 is ready to the ammonia that burns, and in mixing chamber (being called mixing chamber 2 among Figure 10) and through after one the air mixed in the heat exchanger 160 (HE1), mobile ammonia stream through start unit just stops to flow.When the temperature of cracker 110 is high enough to cracking, through opening proportioning valve PV2 ammonia is supplied to cracker 110, and take crackate out of from cracking chamber 110.When 2 approaching the exhausting of the storage unit in the unit 1, a part of hydrogen that is produced can redirect to mixing chamber 1 by passing ratio valve PV1, so that mix mutually with air.When the cracker in the unit 2 110 is ready to burn ammonia, from a part of ammonia-air mixture of mixing chamber 2 via one in the heat exchanger 160 (HE2) combustion chamber 2 that is delivered to unit 2.When the storage unit 2 in unit 1 exhausted, second cracker 110 in the unit 2 was ready to cracking ammonia.When 2 operations of the storage unit in the unit 2, a storage unit 2 of changing in the unit 1 that can enoughly be full of, and when the storage unit in the unit 22 exhausts, can repeat same circulation.
In Figure 10, during operation, each the storage unit module 2 in unit 1 and the unit 2 all has the cracker 110 of insertion.Yet; Shown in figure 11, also can be arranged to guard shield-cracker 110 is separate units, and said separate unit is for example had the vacuum type insulating part of radiation shield isolates well; And the heat of waste gas provides heat energy, so that be delivered to ammonia storage unit or tube 400 in the operation.Can accomplish this heat through heat exchange area and transmit, said heat exchange area is to extend in the storage unit with the similar fashion of inserting cracker 110.What it is contemplated that is, is similar to about combining to be used for the mentioned that kind of external heat exchanger of fuel cell cooling fluid, can be fed to from the hot output gas of guard shield-cracker 110 to be positioned at outside one or more storage units 400.In Figure 11, also show a such embodiment.Waste gas of combustion chamber is transmitted after carrying out heat exchange with the combustion chamber aliment, so that to ammonia storage tube 400 the desorb heat is provided.According to technological requirement, there are one or more storage tubes 400, said storage tube absorbs the heat from the exhaust combustion chamber device.Because burning gases need be under very high temperature conditions (for example in guard shield-cracker 110; Be not less than 300 ℃; But can be higher) requirement of transmitting heat along the whole length of cracking chamber 1, the heat that the heat that in combustion chamber 2, produces is consumed more than ammonia cracking reaction in cracking chamber 1.This has guaranteed in burnt gas, to exist obtainable a large amount of recyclable heat.Yet waste gas of combustion chamber must be higher than 50 ℃, to be used for carrying out heat exchange with storage tube 400 effectively, so that carry out the ammonia desorb.This can be guaranteed through such method; Said method supplies to aliment, the change burning cracking rate of combustion chamber 2 including, but not limited to change, and changes the size that the heat transferred that is used for the waste gas of spontaneous combustion in the future arrives the heat exchanger 160 of the aliment that burns.In said embodiment,, in system, have to only implement a cracker 110 though some storage units 400 are the complete generation hydrogen or the part of electricity generation system 60,70.
What also it is contemplated that is, from the output gas of guard shield-cracker 110 with exchange heat to the heat carrier fluid, said heat carrier fluid with heat delivery to heat-storage unit 400 to be used for desorb ammonia.Figure 12 shows a such embodiment.In the waste gas in the cracker 110 any one or two kinds with heat transferred to the for example circulating fluid of silicone oil, said circulating fluid so with a part of heat transferred to one or more ammonia storage units 400.Heat is carried fluid can at first carry out heat exchange with waste gas of combustion chamber, and carries out heat exchange with cracker chamber waste gas then.After carrying out exchange heat with waste gas of combustion chamber, a part or whole stream can continue to exchange the heat from cracking chamber waste gas.From guard shield-cracker waste gas, reclaim heat and also can take place with opposite order, that is, at first from cracking chamber waste gas, then from waste gas of combustion chamber.System can be combined into one with fuel battery as above paragraph is mentioned, to be used for generating operation.
All documents of being quoted in this manual all are incorporated herein with the mode of quoting such as patent, patent application and journal article full content.
To should be noted in the discussion above that already provided previous embodiment only is the purpose in order explaining, and should not to be interpreted as restriction the present invention.Although reference example property embodiment has explained the present invention, should be understood that used in this article statement is to describe and explanatory statement, and non-limiting statement.Not being contrary in every respect under the prerequisite of scope of the present invention and spirit, can make a change within the scope of the appended claims, like current that state and modification.Although described the present invention with reference to concrete device, material and embodiment in this article, the present invention is not intended to be limited to disclosed in this article concrete example; On the contrary, the present invention extends to all such as function equivalent structure, method and usage in the accompanying claims scope.
Claims (17)
1. one kind generates the reactor (110) of hydrogen based on ammonia, and the said reactor that generates hydrogen based on ammonia comprises:
-ammonia cracking chamber (1), said ammonia cracking chamber has the ammonia Cracking catalyst;
-inner combustion chamber (2), said inner combustion chamber have combustion catalyst or the oxidation catalyst with the thermo-contact of said ammonia cracking chamber;
-ammonia preheating chamber (3); And
-outer shield annular element (6), said outer shield annular element are used for reclaiming heat from the combustion product that leaves said combustion chamber (2),
Wherein, the said outer shield annular element (6) of said cracking chamber (1), said inner combustion chamber (2), said preheating chamber (3) and recovery heat is according to this order arranged concentric, and said cracking chamber (1) forms innermost chamber.
2. the reactor of generation hydrogen according to claim 1 (110), said reactor also comprises: heat exchange fin (10), said heat exchange fin extends to the said cracking chamber (1) from the surface of said combustion chamber (2); And flow distributing hole (5), said flow distributing hole makes it possible to through making ammonia flow through said flow distributing hole (5) ammonia supplied to said cracking chamber (1) equably.
3. system that is used to generate hydrogen, said system comprises at least one storage unit (119,120; 400), said storage unit accommodates the solid-state ammonia storage material (7) that can discharge ammonia through desorb, and said solid-state ammonia storage material is preferably metal amino salt; Said solid-state ammonia storage material is combined at the reactor (110) of when operation and at least one generation hydrogen according to claim 1; Wherein, when operation, at least one waste heat that generates the reactor (110) of hydrogen is passed at least one storage unit (119 of operating; 120,400).
4. system according to claim 3; Wherein, Said at least one storage unit (119,120) has the concentric pipe (8) of hollow, and the concentric pipe of said hollow partly or extends through said unit with connecting; When operation, one in the reactor of at least one said generation hydrogen (110) is inserted in the said unit.
5. system according to claim 4; Wherein, Said solid-state ammonia storage material (7) in one or more storage units (119,120) is as the reactor (110) of the said generation hydrogen of operating down at the temperature conditions that is higher than 300 ℃ and the heat-insulating part between the environment.
6. according to claim 4 or 5 described systems; Wherein, Said one or more storage unit (120) has annular compartment (9) in the outside; Said annular compartment has fluid intake and fluid issuing, and said fluid intake and fluid issuing are used to provide heat with desorb ammonia as heat exchanger.
7. according to any described system in the claim 4 to 6; Wherein, When the reactor (110) of said generation hydrogen when being inserted into; Said one or more storage unit (119,120) has the space (11) between the inwall of the reactor (110) that is positioned at said generation hydrogen and said storage unit (119,120).
8. system according to claim 7; Wherein, The reactor of said generation hydrogen (110) is operated being higher than under 300 ℃ the temperature conditions, wherein, said space (11) can change or said space (11) by the fluid filled that can change; So that control the reactor (110) of said generation hydrogen and the heat transmission between the said storage unit (119,120).
9. according to any described system in the claim 4 to 8, said system also comprises: start unit (170), said start unit are assisted the said combustion chamber (2) of the reactor (110) of the said generation hydrogen of heating; And heat exchanger (160), said heat exchanger reclaim the evaporation heat that is formed on the steam in the said combustion chamber (2) and mixing air and from the ammonia of said storage unit (119,120) to enter into said combustion chamber (2).
10. according to any described system in the claim 4 to 9; Said system comprises two modules, and each said module includes in said at least one storage unit (119,120); Said storage unit has the concentric pipe (8) of hollow; The concentric pipe of said hollow partly or extends through said unit with connecting, and when operation, one in the reactor (110) of said at least one generation hydrogen is inserted in the said unit.
11. system according to claim 3, said system comprises: at least two storage units (400); The reactor (110) of the generation hydrogen of isolating well as one quilt of separate unit; Reactor (110) with the generation hydrogen of isolating well as one quilt of separate unit; The heat that can will be created on from the reactor of said generation hydrogen the said combustion chamber (2) is fed at least two storage units (400) that are positioned at the outside via valve; Perhaps can be fed to heat exchange area; Said heat exchange area extends in the said storage unit (400), and said valve is directed to operating in said at least two storage units (400) in order with combustion product.
12. system according to claim 11; Wherein, The heat of said combustion product is sent to said storage unit (400) via heat exchanger (160); Said heat exchanger will from the combustion product of said combustion chamber (2) and/or from the exchange heat of the crackate of said cracking chamber (1) to circulating fluid, said circulating fluid is sent at least one in said at least two storage units (400) with a part of heat.
13. TRT (60; 70); Said TRT comprises alkaline fuel cell (151) or Proton Exchange Membrane Fuel Cells (152); Said TRT is provided with the absorber (153) that is used to absorb little ammonia and the system of generation hydrogen according to claim 4, and from said system, hydrogen is fed into said alkaline fuel cell (151) or supplies to said absorber (153); And after said absorber (153) absorbed little ammonia, said hydrogen was fed into said Proton Exchange Membrane Fuel Cells (152).
14. TRT according to claim 13; Said TRT also comprises pump (180); The desorption pressures of the said solid-state storage material (7) in said storage unit (2) is lower than and overcomes at the ammonia said TRT (60 of flowing through; During the required stress level of the pressure drop that is produced 70), said pump strengthens flowing of the reactor (110) of ammonia from said storage unit (119,120) to said generation hydrogen.
15. a TRT (60,70), said TRT comprise alkaline fuel cell (151) or Proton Exchange Membrane Fuel Cells (152), said TRT is provided with: at least one absorber (153) that is used to absorb little ammonia; System according to claim 11 or 12 described generation hydrogen; From said system; Hydrogen is fed into said alkaline fuel cell (151) or supplies to said at least one absorber (153); And after little ammonia was absorbed in said at least one absorber (153), said hydrogen was fed into said Proton Exchange Membrane Fuel Cells (152); And pump (180); The desorption pressures of the said solid-state storage material (7) in said storage unit (2) is lower than and overcomes at the ammonia said TRT (60 of flowing through; During the required stress level of the pressure drop that produces 70), said pump strengthens the mobile of the reactor (110) of ammonia from one or more storage units (400) to said generation hydrogen.
16. method of operating the system that generates hydrogen; Said system comprises at least one storage unit (119; 120,400), said storage unit accommodates solid-state ammonia storage material (7); Said solid-state ammonia storage material can discharge ammonia through desorb; Said solid-state ammonia storage material is metal amino salt preferably, and wherein, the waste heat of the reactor of said generation hydrogen (110) is recovered and uses the heat whole or in part desorb is come from the ammonia of said ammonia storage material (7) to be sent to said storage unit (2).
17. method according to claim 16; Said method also comprises through pipe the fuel cell cooling fluid of fuel cell is incorporated into the outer shield of said storage unit (2), and after carrying out heat exchange with said ammonia storage material (7), said cooling fluid is returned.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US30954210P | 2010-03-02 | 2010-03-02 | |
| US61/309,542 | 2010-03-02 | ||
| PCT/EP2011/001046 WO2011107279A1 (en) | 2010-03-02 | 2011-03-02 | Apparatus for generating hydrogen from ammonia stored in solid materials and integration thereof into low temperature fuel cells |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102782921A true CN102782921A (en) | 2012-11-14 |
Family
ID=44041613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800116731A Pending CN102782921A (en) | 2010-03-02 | 2011-03-02 | Apparatus for generating hydrogen from ammonia stored in solid materials and integration thereof into low temperature fuel cells |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP2543103A1 (en) |
| CN (1) | CN102782921A (en) |
| WO (1) | WO2011107279A1 (en) |
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| CN110295372A (en) * | 2019-06-21 | 2019-10-01 | 福州大学化肥催化剂国家工程研究中心 | A kind of ammonia electrolysis hydrogen production device |
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|---|---|---|---|---|
| CN110295372A (en) * | 2019-06-21 | 2019-10-01 | 福州大学化肥催化剂国家工程研究中心 | A kind of ammonia electrolysis hydrogen production device |
| CN110295372B (en) * | 2019-06-21 | 2023-09-12 | 福大紫金氢能科技股份有限公司 | Ammonia electrolysis hydrogen production device |
| CN114797684A (en) * | 2022-04-01 | 2022-07-29 | 众立能源装备(陕西)有限公司 | Hydrogen production device for ammonia gas low-temperature catalytic decomposition |
| WO2023246668A1 (en) * | 2022-06-21 | 2023-12-28 | 福州大学 | Ammonia decomposition reactor having ammonia preheating function |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2543103A1 (en) | 2013-01-09 |
| WO2011107279A1 (en) | 2011-09-09 |
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