CN100540459C - Use the method for temperature swing reforming and solid-oxide fuel cell generating - Google Patents
Use the method for temperature swing reforming and solid-oxide fuel cell generating Download PDFInfo
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- CN100540459C CN100540459C CNB200480014195XA CN200480014195A CN100540459C CN 100540459 C CN100540459 C CN 100540459C CN B200480014195X A CNB200480014195X A CN B200480014195XA CN 200480014195 A CN200480014195 A CN 200480014195A CN 100540459 C CN100540459 C CN 100540459C
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Abstract
The invention provides from the improvement of fuel cell-powered method.Periodically reforming process is also referred to as temperature swing reforming, provides effective production method in order to produce used hydrogen containing synthesis gas in the solid-oxide fuel cell application.In one embodiment, synthetic gas that at least some at first produce in the temperature swing reforming process and air combustion, thus provide heat for the regeneration step of temperature swing reforming process.The synthetic gas that produces among the TSR is particularly suitable for solid-oxide fuel cell and uses.
Description
Invention field
The present invention relates to improving one's methods and purposes fuel cell from hydrocarbon fuel hydrogen manufacturing.More specifically, the present invention relates to a kind of method, wherein synthetic gas and solid-oxide fuel cell (" the SOFC ") coupling that produces in the periodicity reforming process.Periodically reforming process is called " temperature swing reforming " or abbreviates " TSR " as.In temperature swing reforming, be regeneration step after the synthetic gas reforming step.The hydrogen stream that TSR produces is particularly suitable for SOFC, and its temperature is of value to that types of fuel cells.In preferred embodiments, TSR and SOFC physics are integrated, thereby have improved the total efficiency of system.The invention provides a kind of from the hydrocarbon being the effective ways of the fuel cell system power supply of fuel, be particularly useful for limited application scenario, space, as the application scenario of " vehicle-mounted (the formula) " vehicles (for example passenger vehicle, truck, motorbus etc.) and distributed energy system.
Background of invention
Solid-oxide fuel cell all has application prospect for multiple energy apply, comprises that distributed energy produces and vehicular applications.Existing SOFC system can operate than polymer dielectric or under the temperature that directly the alcohol fuel battery system is higher basically, and it can bear 1000 ℃ high temperature.Yet SOFC more has endurance basically for common contained " impurity " gas in the hydrogen fuel, particularly when generating foreign gas from the hydrocarbon source.The present invention is integrated with temperature swing reforming and solid-oxide fuel cell, thereby effective energy production method is provided, and can be the common hydrocarbon fuel fuel supplying.
Conventional method for syngas generation comprises steam reformation, the gas-phase partial oxidation automatic thermal reforming.Every kind of method all has merits and demerits separately.
In the steam reformation process, steam and hydrocarbon-bearing material reaction obtain hydrogen-rich synthetic gas.According to methane, general chemical formula is:
CH
4+H
2O→CO+3H
2(1)
Usually, excess steam is used for pushing balance to the right side.In hydrogen produced, excess steam always was used to improve the aqueous vapor mobile response:
CO+H
2O→CO
2+H
2(2)
Because reaction height heat absorption, steam reformation are carried out in big stove usually, wherein reforming catalyst is contained in the pipe.This pipe must be able to bear the elevated pressures of the synthetic gas that obtains, and can conduct heat when about 1000 ℃ temperature simultaneously.As described in the Stanford Research InstituteInternational Report No.212 (1994), steam reformation process efficiency (divided by the combustion heat of reformation material and stove fuel come with the combustion heat of hydrogen fixed) is for about 74%, and air speed (is defined as per hour C
1The ft of the standard cubic foot/catalyst bed of-material of equal value
3) be about 1000hr
-1Unfortunately, steam reforming furnace accounts for very big spatial volume, basically greater than pipe volume.This feature and relatively low efficient have seriously limited its purposes in fuel applications (as fuel cell), and might be able to not be used for using with the vehicles or the distributed energy on floor.
Sederquist (United States Patent (USP) 4,200,682,4,240,805,4,293,315,4,642,272 and 4,816,353) has instructed a kind of steam reformation process, wherein by providing the heat of reforming in round-robin burning and reformation step cycle in bed.As described in Sederquist, the high quality recovery of heat in the bed of reforming can make theoretical efficiency reach about 97%.Yet, these patent disclosures under the utmost point poor efficiency method of operating, and air speed is about 100hr
-1(press C
1-material of equal value).A kind of result of low-speed is, the thermal losses height, thereby overslaugh they have greater efficiency.The invention solves this problem.
The inventor discloses a kind of method of producing hydrogen from hydrocarbon containing fuels, and has obtained high efficiency energy generation system with the solid-oxide fuel cell coupling.
Summary of the invention
The invention provides a kind of method improvement from fuel cell manufacture electric power, wherein fuel cell acts as a fuel with the hydrocarbonaceous synthetic gas.Periodically reforming process is also referred to as temperature swing reforming, and a kind of effective means of fuel cells applications production hydrogen containing synthesis gas that is is provided.Compare with conventional oil treater/fuel cell system, temperature swing reforming and solid-oxide fuel cell coupling have realized heat and material efficiency.In one embodiment, temperature swing reforming method and SOFC physical bond.This combination design has obtained higher system efficient.Specific embodiments hereinafter is described.
Hereinafter the temperature swing reforming of Xiang Xishuominging generally includes:
(a) with 500hr at least
-1C
1The GHSV air speed is introduced first end that the streams that contains hydrocarbon and steam is passed through first district, and contain a packing material and introduces steam reforming catalyst in described first district, and they are heated to reforming temperature, contain H with production
2, CO and CO
2Synthetic air;
(b) first end by second district makes at least a portion product of step (a) pass through second district of containing a packing material, and heat is passed to packing material from synthetic air;
(c) remove all products from described second district basically by second end in second district;
(d) oxygen-containing gas is introduced second end in described second district;
(e) described oxygen-containing gas is contacted with fuel, and make described gas and fuel combustion with the contiguous location of described first district and the described second regional boundary face, thereby to reforming temperature and produce waste gas, described waste gas is by first end disengaging in described first district with described first district's reheat.Method recited above, wherein the condition of reorganization comprises that at least a portion of reforming catalyst is heated to 700 ℃～2000 ℃ temperature, and step (d) and (e) in fuel supply by at least a portion synthetic gas of described method steps (c).Method recited above also comprises, measures at the interface or basically at the interface temperature of described first district and second district, in case arrive predetermined first temperature, just described oxygen-containing gas introduced described second district; With the temperature around described first district of measurement first end,, just described hydrocarbon-bearing material and steam material are introduced first end in described first district in case arrive predetermined second temperature.Method recited above also comprises, measure described first district and second regional boundary face temperature on every side, in case arrival preset temperature, just begin regeneration step (d), with the temperature around described first district of measurement first end, in case arrive the second predetermined temperature, just begin to reform and recycling step (a), (b) with (c).Method recited above also comprises, wherein operate two or more reactors simultaneously, make step (a), (b) and (c) at least one reactor, carry out, and step (d) and (e) carrying out in another reactor at least, thereby provide continual basically reformate stream to described fuel cell.
By long-pending air speed (the i.e. 500hr at least that calculates of total bed surface
-1).Temperature swing reforming method production hydrogen containing synthesis gas effectively, it can be used as the fuel of high-temperature fuel cell, normally solid-oxide fuel cell.
Solid Oxide Fuel Cell (SOFC) is made by solid-state material usually, and wherein ionogen generally comprises the ionic conductivity ceramics oxide compound.In other fuel cells, SOFC is grouped into by three kinds of one-tenth: negative electrode, anode and be sandwiched in therebetween ionogen.Anode among the SOFC is to conduct oxygen or hydrionic solid, but the most common conduct oxygen ions.Airborne oxygen is separated to become O in cathodic reduction then
=These ions arrive anode by ionogen, there be transported to the anodic fuel reaction.Fuel (for example hydrogen) is by the oxonium ion oxidation, and discharges electronics to external circuit, thereby produces electric power.That is, the anode that the described reformate of step (c) is supplied to solid-oxide fuel cell is with power supply, and its further feature is under greater than 200 ℃ temperature, will contain hydrogen, CO, CO
2, hydrocarbon and steam reformate be supplied to described anode of fuel cell, thereby described reformate further reformed, and hydrogen-rich synthetic gas is supplied to the anode of described fuel cell.Electronics returns negative electrode then, produces the cycle thereby constitute electric power.Each battery can be connected on and produce high-voltage together, and the voltage that each battery produces usually is 0.5～1.2V.The simple reaction that with hydrogen is fuel oxidation thing ionic conduction fuel cell can be expressed as follows:
Negative electrode 1/2O
2+ 2e
-→ O
=
Anode H
2+ O
=→ H
2O+2e
-
Total 1/2O
2+ H
2→ H
2O
Oxide ion is relatively large, is 1.4 dusts, and this needs enough heat energy with fully diffusion in solid electrolyte.Oxide ion SOFC operates being higher than under 600 ℃ the temperature usually, is generally 700 ℃ to 1000 ℃ most.The present invention relates to TSR with the SOFC coupling of oxide ion conduction.That is, from the improving one's methods of fuel cell manufacture electric power, described periodicity reformation processing unit and described solid-oxide fuel cell are comprised jointly and the effluent of wherein said regenerative process provides power with generating to turbine provided by the invention.
Describe exemplary embodiment of the subject disclosure below in detail.
Brief Description Of Drawings
Fig. 1 a and 1b illustrate schematically the reformation and the regeneration step of temperature swing reforming.
Fig. 2 illustrate schematicallys and uses the system of double bed band valve to carry out temperature swing reforming.
Fig. 3 illustrate schematicallys the method design of temperature swing reforming in solid-oxide fuel cell is used.
Fig. 4 illustrate schematicallys the selectable method design of temperature swing reforming in solid-oxide fuel cell is used.
Fig. 5 illustrate schematicallys temperature swing reforming comprises the common property generating apparatus in solid-oxide fuel cell is used method design.
Describe in detail
Fig. 1 shows the basic two step cycles of temperature swing reforming.Referring now to Fig. 1 a and Fig. 1 b, shown first district, or reformer section (1), being also referred to as change bed reformer, second district, or re-heat district are also referred to as synthetic gas recuperator (7).The bed in these two districts all comprises packing material, and the bed of reformer section (1) comprises catalyst for steam reformation.Although reformer section and re-heat distinguish among the figure, should be appreciated that the temperature swing reforming device can comprise a reactor, and this device can combine with the solid-oxide fuel cell device physical.
As shown in Figure 1a, when cycle first step (being also referred to as first reforming step), reformer section (1) is in about 100 °～about 1600 ℃ high temperature, and the temperature of re-heat district (7) is lower than reformer section (1).Hydrocarbon-bearing material is added to first end (3) of reformer section (1) by conduit (15) with steam.Hydrocarbon can be any material of steam reforming reaction that can absorb heat, and comprises methane, petroleum gas, petroleum distillate, kerosene, rocket engine fuel, oil fuel, domestic fuel oil, diesel-fuel, gas oil plant and gasoline.Material also can comprise alcohol, as methyl alcohol, and ethanol etc.Preferably, hydrocarbon be gaseous material or in introducing reformer section (1) after the material that can vaporize fast.Preferably, steam is directly proportional with the amount of hydrocarbon, and (consider only has carbon to steam and carbon ratio example in the hydrocarbon, at CO or CO for about 1 to about 3
2There is not carbon in the material).
Streams is heated (promptly from the bed heat absorption), and changes into synthetic gas by catalyzer.Along with step is carried out, according to the heat transfer property generation thetagram (23) of system.This thetagram generally includes the gradient from the low temperature (100～700 ℃) of reformer inlet to reformation bed tempertaure (about 800 ℃～about 1600 ℃).When bed was designed to have enough heat-transfer capabilities, as described herein, this graphic representation had sharp-pointed relatively thermograde, and along with step is carried out, its gradient moves in reformer section (1).
Synthetic gas is by pyritous second end (5) bed (1) of break away from reforming, and by re-heat district (7), thereby enters and break away from from second end (9) from first end (11).It is lower when re-heat district (7) begins than reformer section (1) temperature.When synthetic gas during by re-heat district (7), synthetic gas is cooled to basically contiguous this and distinguishes the temperature of second end (9), the temperature of the regeneration feed of introducing by conduit (19) in this temperature and cycle second step is roughly the same (to be temperature about 200 ℃～about 1,000 ℃, preferred about 400 ℃～about 600 ℃).Along with synthetic gas cools off in re-heat district (7), produce thermograde (24), and in this step, in re-heat district (7), move.
In the time of between step, thermograde moves between reformer section (1) and re-heat district (7) basically.The size of regulatory region makes gradient move in each district with the comparable time in above-mentioned reforming step.Existing, re-heat district (7) are in high temperature, and reformer section (1) is in low temperature, except thermograde is adjacent to the thermograde of disengaging when respectively distinguishing.It (is that temperature is 20 ℃～1000 ℃ that the temperature of the reformer section (1) of neighboring entry end (3) is cooled to the temperature of being close to the hydrocarbon material that enters by conduit (15) now, about 100 ℃～about 700 ℃, preferred about 200 °～about 600 ℃, most preferably from about 300 ℃～about 500 ℃).
In temperature swing reforming is implemented, use selectable device to measure the termination of reforming step.When reforming step stops carrying out, the temperature of the end of reformer section (5) is lowered, thereby the reformation degradation is lower than acceptable transformation efficiency.Herein, the reformation performance refers to that the material hydrocarbon changes into gas composition (H
2, CO and CO
2).Herein, the term percent conversion changes into synthetic gas material (CO and CO according to material hydrocarbon metallic substance
2) percentage recently calculate.Herein, the unconverted product hydrocarbon of term refers to not be gas composition (H
2, CO and CO
2) product hydrocarbon metallic substance.These generally include product methane, and the split product of material hydrocarbon and material hydrocarbon.The reformation performance changes to when being lower than acceptable bottom line, and reforming step finishes.In the reality, optimize overall reform and synthetic gas utilizes process will reach the reformation transformation efficiency of required mean time of level.Mean time level the reformation transformation efficiency usually greater than 80%, be preferably greater than 90%, most preferably greater than 95%.
Time point when reforming step finishes, so the process time of reforming step can (a) be selected according to the reaction that in each reforming step time of reformer is changed performance; Or (b) according to totally (mean time) performance or system are selected; Or (c) be fixed as constant reforming step process time or its combination.In embodiment (a), at least one feature of monitoring and reformation performance relating operation.This feature can be a kind of component, as CH
4, H
2, or CO, perhaps selectively be a kind of temperature, as hold the temperature of (5) at the bed of reforming.In one embodiment of the invention, when the temperature of the bed end (5) of reforming was reduced to about 700 ℃～about 1200 ℃ preselected temperature, reforming step finished.In embodiment (b), regulate the process time of reforming step based on the measurement features of overall (mean time) performance that reflects system.This feature can be the average product component, as CH
4, H
2, or CO.In alternate embodiment of the present invention, based on CH in the product
4Time average concentration regulate the process time of reforming step, and use control method as known in the art to shorten or prolong the process time of step, to obtain the CH of intended target
4Amount.In the present embodiment preferred variation, target CH is set
4Amount accounts for about 1% to about 15% of hydrocarbon pledge material carbon.In embodiment (c), the process time of reforming step is a regular length, and its value is acceptable for the operation air speed.In one embodiment of the invention, the process time of reforming step is fixed as about 0.1 second extremely less than about 60 seconds, and preferred about 1.0 to 30 seconds.
Disengaging conduit (17) at second end (9) by re-heat district (7) is collected the synthetic gas place, and second step in beginning cycle is also referred to as regeneration step.Regeneration step shown in Fig. 1 b is delivered to reformer bed (1) with heat from recuperator bed (7).Thereby thermograde 25 and 26 moves between each, and they are with the gradient 23 in the reformation is similar with 24 but direction is opposite.In preferred embodiments, by conduit (19) oxygen-containing gas and fuel are introduced second end (9) in re-heat district (7).This mixture flows through re-heat district (7), and locates burning basically at the interface (13) of two districts (1) and (7).The adjacent domain that burning is preferably located at the interface (13) of re-heat district (7) and reformer section (1) takes place.Among the present invention, term " adjacent domain " refers to that regeneration step combustion will realize the zone of the TSR bed of following two targets: (a) heated reformate district, and make end (5) temperature of reformer section be at least 800 ℃, preferably when finishing, regeneration step is at least 1000 ℃; (b) the re-heat district is cooled to sufficient temp, thereby the heat content of synthetic gas is accepted in performance in reforming step subsequently.Depend on concrete regeneration embodiment, can account for 0% of re-heat district (7) volume～about 50%, can account for 0%～about 50% of reformer section (1) volume with the adjacent domain at interface.In the preferred embodiment of the invention, the regeneration step combustion greater than 90% takes place in the adjacent domain at interface, and regional volume accounts for re-heat district (7) volume less than about 20%, accounts for reformer section (1) volume less than about 20%.
Burning position can be fixed or is fixed on basically the interface (13) in two districts by introducing a kind of combusting component (for example fuel), and another kind of composition (for example oxygen-containing gas) can be introduced at first end (9) of re-heat district (7).Selectively, fuel and oxygen-containing gas (19) stream can mix at the opening end (9) of re-heat district (7), and by the re-heat district, locates burning at the interface (13) in two districts.In this embodiment, by temperature, the time, burning position is controlled in hydrokinetics and katalysis.Fuel and oxygen usually need with the spontaneous combustion time of temperature correlation, to burn.In one embodiment, the mobile thetagram that will set up in the re-heat district (7) of the non-combustion mixt in regeneration step first substep, thus arriving at mixture before the interface in two districts, its temperature of re-heat district is not enough to spontaneous combustion.
In reformer section, exist catalyzer also to be used in that position and cause burning, and increase and the design space,, and burning is limited in the zone contiguous with above-mentioned interface with further stable burning process in the space in reformer section and re-heat interval.In another embodiment, fix the incendiary position by Machine Design re-heat district.In this design, fuel and oxygen-containing gas in different passages by (figure does not show), thereby prevent burning, mix at the interface (13) in two districts up to material.In this position, flame holder in the reformer section (figure does not show) or catalyzer can be used for causing burning.
The burning of fuel and oxygen-containing gas produces hot waste gas, when waste gas can heat it during by reformer section (1).Waste gas breaks away from by conduit (27) through first end of reformer section (3) then.Regulate the composition of oxygen-containing gas/fuel mixture, to provide reformer section required temperature.Can regulate composition by regulating in the mixture combustible portion with the ratio of flammable part not, thus attemperation.For example, non-combustible gas is as H
2O, CO
2, and N
2Can be added in the mixture, to reduce temperature of combustion.In preferred embodiments, by using steam, waste gas, or reducing air is as a kind of composition of mixture and obtain non-combustible gas.When the thermograde in the hot waste gas arrival reformer, bed is passed in the further activity of gradient.The temperature in of waste gas is substantially equal to the temperature of the reformer section (1) of neighboring entry end (3).When regeneration step began, temperature in was substantially equal to the temperature in of the reformation material of aforementioned reforming step.Along with the carrying out of regeneration step, when thermograde arrival was not held (3), temperature in slowly increased then apace, and the reformation temperature of charge is high 50-500 ℃ in the time of can finishing than step.
Now, reformer section is in the reforming temperature that is suitable for catalytic reforming once more.
In transformation is reformed enforcement, use selectable device to measure the termination of regeneration step.Reform bed when carrying out reforming step when enough heats are supplied or transfer to, and regeneration step finishes.Time point when regeneration step finishes, so the process time of regeneration step can (a) be selected according to the reaction that in each regeneration step time of PSR is changed performance; Or (b) according to totally (mean time) performance or system are selected; Or (c) be fixed as constant regeneration step process time.In embodiment (a), some features of monitoring and regenerability relating operation.This feature can be a kind of component, as O
2, CH
4, H
2, or CO, perhaps can be a kind of temperature, as hold the temperature of (3) at the bed of reforming.In one embodiment of the invention, when the temperature of the bed end (3) of reforming was brought up to about 200 ℃～about 800 ℃ preselected temperature, regeneration step finished.In embodiment (b), regulate the process time of regeneration step based on the measurement features of overall (mean time) performance that reflects system.This feature can be the average product component, as CH
4, H
2, or CO, or some other system metrics value.In one embodiment of the invention, based on CH in the product
4Time average concentration regulate the process time of regeneration step, and use control method as known in the art to shorten or prolong process time, to obtain the CH of intended target
4Amount.In preferred embodiments, target CH is set
4Amount accounts for about 1% to about 15% of hydrocarbon pledge material carbon.In embodiment (c), the process time of regeneration step is a regular length, and its value is acceptable for the operation air speed.In one embodiment of the invention, the process time of regeneration step was fixed as about 0.1 second to about 60 seconds, and preferred about 1.0～30 seconds.In all these embodiments, but especially in embodiment (c), preferably also regulate the regeneration step flow velocity, to improve or to be reduced in amount of heat-its mode that is added in the step on the bed similar to described mode of regulate process time in embodiment (b).In another embodiment of the invention, the regeneration step process time is fixed as about 1 second to about 60 seconds, and regulates the regeneration step flow velocity in time, makes CH in the reformate
4Time average concentration adjacent objects CH
4Amount, target CH
4Amount accounts for about 1% to about 15% of hydrocarbon pledge material carbon.
The common Hour of the air speed of system is expressed as the cumulative volume of the standard volume gas flow rate of material divided by catalyst bed, is called gaseous state time and space speed, or " GHSV ".Air speed also can become to assign to respect to the hydrocarbon of material to define.According to definition, the GHSV of methane material is that the standard times volumes of gas flow velocity of methane is divided by bed volume.Herein, the term air speed is abbreviated as GHSV, refers to the air speed of any hydrocarbon material by C.Equally, the speed of hydrocarbon material is pressed the mole velometer and press the standard volume velometer of carbon material, just look like carbon be that the gaseous state thing is held.For example, its average carbon value of gasoline material is 7.0, and with 1, the gaseous flow rate of 000NL/hr flows to the 1.0L bed, thereby air speed is 7,000.This definition is based on the Flow of Goods and Materials in the reforming step, and wherein bed volume comprises all catalyzer and heat transfer solids in reformer section and the re-heat district.
In temperature swing reforming, air speed, C
1GSHSV, be generally about 500～about 150,000, preferred about 1,000～about 100,000, most preferably from about 2,000～about 50,000.
In preferred embodiments, under bed packing and air speed condition, carry out temperature swing reforming, thereby enough rates of heat transfer are provided, it is characterized in that heat transfer parameter, Δ T
HT, be about 0.1 ℃～about 500 ℃, more preferably from about 0.5 ℃ and 40 ℃.Parameter Δ T
HTBe the volumetric heat transfer coefficient h of required bed average-volume rate of heat transfer H of reformation and bed
vRatio.The required volumetric heat transfer speed of reforming is by air speed and reformation heat (heat/C
1Volume) product calculates.For example, H=4.9cal/cc/s=2.2cal/cc*8000hr
-1/ 3600s/hr, wherein 2.2cal/cc is the heat per standard volume methane of methane reforming, the 8000th, the C of methane
1GHSV.When the process time comparability of reforming step and regeneration step, the H value in two steps also can be compared.The volumetric heat transfer coefficient h of bed
vCan be by technical measurement well known in the art, and press area base system number (cal/cm for example usually
2S ℃) and heat transfer ratio surface-area (a
v, cm for example
2/ cm
3) product calculate, be commonly referred to the wetting areas of packing.
TSR carries out under about 0～about 20 atmospheric pressure usually.The cycleoperation of TSR is generation time difference between reformation cycle and regeneration period, and the preferred time isolates.Allow like this to operate reforming step being different under the pressure of regeneration step.In preferred embodiments, reforming step is preferably carried out under about 0～about 5 normal atmosphere, and regeneration step is carried out under about 0～about 4 normal atmosphere.Also preferably carry out reforming step under the pressure higher than regeneration step, the pressure difference between these two steps is more preferably less than 1 normal atmosphere preferably less than 5 normal atmosphere.Use high pressure ratio more favourable, for example, when fuel cell TSR system links to each other with turbine or other this power generating devices.
Select the packing material of bed, make its heat transfer characteristic can keep high-speed.As known in the art is that the bed packing can (be commonly referred to wetting areas, a with heat transfer coefficient (h) and heat transfer surface area
v) characterize.For gas and solid property, the mutual relationship of these parameters is known.The product of these two parameters is heat transfer coefficients (by bed volume) of bed:
Volumetric heat transfer coefficient:
Heat transfer coefficient is responsive for all gases character, comprises flow velocity and composition.Coefficient in reformation is higher usually, because the hydrogen of gas has high thermal conductivity.Usually can enhancement coefficient (for example, 1/8 " its h of particle by the characteristic size that reduces packing
vThan 1/2 " particle is higher).
The heat of measuring hydrocarbon reforming also is known, and can be that unit expresses by the heat of the appropriate hydrocarbon gas of every standard volume.The heat transfer requirement of TSR system can be expressed as the volume heat of reformation and the product of the GHSV of material.
The volumetric heat transfer requirement of system is expressed as:
In this equation, GHSV and Δ H
REFHas substantially the same inventory unit.Therefore, if the unit of GHSV is the C of every L bed
1NL/hr, Δ H so
REFUnit be every C
1The heat of reaction of NL.
Also use heat transfer δ-temperature Δ T herein,
HTCharacterize the TSR system.Δ T
HTBe defined as the ratio of volumetric heat transfer requirement and volumetric heat transfer coefficient.
Characteristic heat transfer Δ T
HT=H/h
v
Characteristic Δ T
HTShown the difference between the heat transfer supply and demand.Based on general regeneration step condition, use heat transfer coefficient to calculate Δ T herein,
HTCharacteristic Δ T
HTIt is design variable of the present invention.Select packing or air speed to satisfy Δ T of the present invention
HTDemand.
Δ T of the present invention
HTBe about 0.1 ℃ to about 500 ℃.More preferably, characteristic Δ T is about 0.5 ℃ to 40 ℃.For example, if the heat transfer coefficient of packing is 10BTU/ft
3S °F, suppose that so the reforming methane heat is 248BTU/scf, at characteristic Δ T
HTWhen being 40 ℃, C
1GHSV is 1.5 * 10
4Hr
-1Suppose that a bed packing material is as known in the art, comprise granule packaging, foam and cellular monoblock material, the present invention can be about 100 in air speed so, 000hr
-1In time, operate efficiently.
In preferred embodiments, the bed packing material has several characteristic.It has following ability: recirculation between high temperature (for example 〉=1000 ℃) and low temperature (for example≤600 ℃), provide high wetting areas (for example 〉=6cm
-1) and volumetric heat transfer coefficient (for example 〉=0.02cal/cm
3S ℃, preferably 〉=0.05cal/cm
3S ℃, most preferably 〉=0.10cal/cm
3S ℃), to flowing resistance low (being low pressure drop), have with regeneration step in top temperature uniform operation temperature, for thermal shocking higher resistance is arranged.In addition, preferably material have higher volumetric heat capacity (for example 〉=0.10cal/cm
3℃, preferred 〉=0.20cal/cm
3℃).In addition, the bed packing material can support the reforming catalyst in the bed of reforming fully.Can satisfy these requirements by shape, size and the composition of control bed packing material.
The heat-transfer capability and the resistance to flow of the shape and size influence bed of bed packing material.This is because how the shape and size of packing influence liquid by packing, comprises size and turbulent flow in the liquid boundary layer, and they are main resistances of heat, quality and momentum transfer between liquid and solid.In addition, the size of material also influences the resistance of bed to thermal shocking, because bigger structure is easy to thermal shocking usually.Shape influences a thermal capacitance by its relation with the cavity volume of bed.Design favourable package shape to realize that these aspects of the present invention are known in the art.
The example of the packing material that is fit to comprises cellular monoblock material and the mobile monoblock material of wall, and they have straight channel, thus minimum pressure drop, and keep bigger reactor length.Preferred cellular its channel density of monoblock material of the present invention is about 100 passage/in
2To about 3200 passage/in
2(15-500 passage/cm
2).In selectable embodiment, can use more zigzag packing, as the bed of foam monoblock material and packing.Its hole density of preferred foam monoblock material of the present invention be about 10ppi (hole/inch) to about 100ppi (be 4-40 hole/cm).It is about 180ft that the present invention preferably packs its infiltration surface-area of bed
-1To about 3000ft
-1(be 6-100cm
-1).
At service temperature and thermal shocking resistance, select the composition of bed packing material.The thermal shocking resistance is usually for the material maximum with relatively low thermel expansion coefficient, because when temperature during with circulation change, its size occurrence temperature inductive changes.The stupalith that temperature of combustion and thermal shocking is had resistance is preferred.Cordierite material (magnesium aluminum silicate) is preferred, because their thermal expansivity is extremely low.Other preferred construction materials comprise aluminum silicate clay, as kaolin, are mixed with the aluminum silicate clay of aluminum oxide, or are mixed with the aluminum silicate clay and the aluminum oxide of silicon oxide and selectable zeolite.Other structured materials that are fit to comprise mullite, aluminum oxide, and silica-alumina, zirconium white, and common any inorganic oxide material, or at least 1000 ℃ of following stable other materials.These materials can use separately or mix use, and for example can make their Stability Analysis of Structures by rare earth addition.The bed packing material of breeding blanket can be identical or different with the packing material of reformer section.
Bed structure in reformer section and the re-heat district can use various ways as known in the art.Acceptable structure comprises horizontal beds, vertical bed, radial bed and concentric ring bed.Be packaged in the design be can be monolithic or particulate state.Granule packaging can liquefy in some step of the present invention.In preferred embodiments, the bed packing is a fixed sturcture.
The reforming catalyst that is fit to comprises precious metal, transition metal and group VIII metal ingredient, and Ag, Ce, and Cu, La, Mo, Mg, Sn, Ti, Y and Zn, or its combination, and add other metals and the non-metallic material that can stablize and/or strengthen catalytic performance.Herein, the term composition relates to metal or metal oxide.Preferred catalyst system comprises Ni, NiO, Rh, Pt, and combination.These materials can deposit or be coated on the support of the catalyst well known in the art or among.
Fig. 2 shows the embodiment of temperature swing reforming, illustrate schematicallys reforming with recycle and regenerative process.In this embodiment, use two temperature swing reforming bed systems simultaneously, thus a system reform, and another system regenerates.Although each cyclical operation is to use a plurality of beds can make the product continuous flow of reformation basically.In Fig. 2, first (220) are used for regeneration step, and second (230) are used for reforming step.Each bed (220 and 230) all comprises reformer section and re-heat district.In this embodiment, several sleeving valves are used to be controlled at flowing back and forth between each.First sleeving valve (257 and 259) is used to control hydrocarbon material and steam material to each flow, and second sleeving valve (252 and 254) is used for controlling the product of reforming step and breaks away from from the re-heat district.The 3rd sleeving valve (251 and 253) is used to regulate oxygen-containing gas/fuel and selectable incombustible gas to each flow, and quadruplet valve (256 and 258) is used to control waste gas and breaks away from from reformer section.
In operation, when valve (251), (254), (256) and (259) are when opening, valve (252), (253), (257) and (258) are closed.When these valves were handled this state, oxygen-containing gas and fuel (219) entered bed (220) by valve (251), and waste gas (227) breaks away from bed (220) by valve (256).Simultaneously, hydrocarbon and steam material (215) enter second (230) by valve (259), and reformate (217) breaks away from bed (230) by valve (254).When this step finishes, valve (252), (253), and open (257) and (259), valve (251), (254), (256) and (257) are closed, above-mentioned circulation reverse, i.e. first (220) reformation material, second (230) reactivation heat.
Fig. 3 illustrate schematicallys above-mentioned temperature swing reforming process hydrogen fuel is supplied to solid-oxide fuel cell.TSR unit (300) can comprise a bed, or preferably includes a plurality of beds.In selectable a plurality of embodiments, the unit comprises valve and flow control in (300), and does not show in the drawings.This form and function are described with reference to figure 2.With reference to figure 3, hydrocarbon-bearing material (301) is supplied to the reformer section of TSR reactor (300) as gasoline and steam (305).Use above-mentioned temperature swing reforming process that hydrocarbon-bearing material gas is become synthetic gas with steam reforming.Synthetic gas (302) generally includes CO, CO
2, H
2, H
2O and residual hydrocarbon gases.The temperature of the synthetic gas that TSR makes is about 200 ℃～about 800 ℃, preferred about 300 ℃～about 600 ℃.The inlet pressure of the synthetic gas that TSR makes is about 0 normal atmosphere～about 25 normal atmosphere, preferred about 0 normal atmosphere～about 5 normal atmosphere.
Hydrogen containing synthesis gas (302) is supplied to anode of fuel cell.In preferred embodiments, the anode region of SOFC, especially battery, operation at high temperature, about 600 ℃～about 1200 ℃ usually.CO and residual hydrocarbon in the synthetic gas (302) are further reformed at the anode region of SOFC, thereby further increase the hydrogen richness of fuel.Hydrogen-rich synthetic gas is supplied to anode of fuel cell, and hydrogen richness wherein is used as the fuel of electrochemical reaction there, and produces electric power.The synthetic gas that the rich hydrogen of term refers to have additional hydrogen content is in this embodiment by reform once more at the anode region of SOFC steam and CO, CO
2And residual hydrocarbon, or its mixture preparation.Oxygen-containing gas (306) is pressed the air supply usually, is provided to the negative electrode of SOFC (310).The SOFC electrochemical reaction takes place in hydrogen-rich synthetic gas " fuel ".The SOFC oxonium ion by intensive ionogen be transmitted with anodic proton chemical combination.Close along with electronegative oxonium ion and hydrogenation and produce H
2O, anodic oxonium ion supplies electrons, electronics turns back to the negative electrode of electron deficiency by external loading.Anodic effluent (303) comprises CO, CO
2, the water that generates in the reaction (or steam) reaches any residual hydrogen that fuel cell does not consume.In preferred embodiments, the residual fuel content in the effluent is used for the fuel of above-mentioned TSR regeneration step.Therefore, effluent (303) is divided into two kinds of logistics (304) and (305) at least, and wherein materials flow (304) comprises enough fuel, thereby can finish the combustion step of above-mentioned TSR regeneration step, logistics (305) comprises enough water-contents, thereby to TSR process supply reformation steam.
In preferred embodiments, negative electrode effluent (307) is used for the TSR regenerative process, and the air of introducing negative electrode is enough to supply the oxygen demand of SOFC negative electrode, and can be used as the oxygenant of above-mentioned TSR regeneration period.That is, fuel cell cathode flow goes out thing the described fuel of at least a portion and oxygen-containing gas is supplied to step (d) and (e) in the temperature swing reforming of the present invention.Usually, contain oxygen source of supply (306) and be included as the gas of oxygen stoichiometry amount about 1.2～2.0, be preferably 1.2～1.5 the oxygen excesses about 20%～about 100% of negative electrode supply (promptly) at the SOFC negative electrode.That is, fuel cell cathode flow goes out thing the described oxygen-containing gas of at least a portion is supplied to the location of contiguous described first district and the second regional boundary face, is used for the step (d) of temperature swing reforming of the present invention and (e).
Although be to illustrate according to physically separating, in preferred embodiments, TSR (300) and SOFC (310) comprise the device of one physically.The advantage of integrated device comprises the minimizing or the cancellation that can improve heat integration, liquid water collection and storing unit and fast SOFC is heated to suitable service temperature.In the system of physics one, the input and output of TSR reactor and SOFC directly are connected with logistics except heat exchange.The oxygen source of TSR is by cathode exhaust (logistics 307) transmission.The SOFC anode directly uses TSR reformation effluent, and without further processing.Anode effluent (303) is directly as the vapour source (305) of reformer and the fuel source (304) of TSR regeneration step.That is, the anode of fuel cell effluent is with the step (a) of at least a portion steam supply to the temperature swing reforming of the present invention.When two processes of such set, except selectable heat exchange, do not need pilot process.So just avoided the complexity of other processes, as water condensation, the aqueous vapor body moves, and hydrogen separates, or carbon monoxide removal.Fig. 3 has shown the embodiment of a kind of direct-connected TSR-SOFC, does not wherein show selectable heat exchange.The physical set of process makes each unit can place same adiabatic system, thereby makes subsidiary conduit, insulation and other size of component minimums.In this embodiment, the TSR process is carried out with the pressure approximately identical with SOFC.
Embodiment 1
The following examples are used for illustrating better each side of the present invention.A certain amount of methane is as the material of incorporate TSR/SOFC shown in Figure 3 system.Shown in the result be at the about 8000C of methane material
1GHSV and 3-TSR second cycling time.The steam/carbon ratio of reformation side is about 1.5.Hydrogen availability in the fuel cells is about 0.8, and the CO availability is about 0.39.In general operation, hydrogen availability and H
2With relative reaction rate/availability of CO with the type of fuel cell membrance chemistry, temperature and other battery parameters change.Logistics (303) about 53% separately enters (305), and about 47% enters (104).Important operation and process parameter are listed in the table below in 1.
Table 1
| Logistics gmols | 301 reform supplies | 302 reform exports | 303 SOFC-outlet | FC-H2-rx | 305 Rfm-Rcy | 304 regenerated fuels | 307 negative electrode effluents | 308 regeneration effluents |
| Temperature ℃ P normal atmosphere | 500 0.5 | 542 0.3 | 527 0.2 | 0.2 | 0.2 | 0.2 | 504 0.1 | |
| CH 4 H 2O | 4.07 0 | 0.12 2.73 | 0.12 13.05 | 0 0 | 0.05 6.19 | 0.07 6.86 | 0 8.46 |
| H2 CO CO 2 N 2 O 2 (mols) | 0 0 0 0 0 | 12.9 6.13 1.41 0.15 0 | 2.58 3.72 3.83 0.15 0 | 12.73 0 0 0 0 | 1.22 1.76 1.82 0.07 0 | 1.36 1.96 2.01 0.08 0 | 30.75 1.79 | 0 0 3.97 30.73 0.01 |
| 4.07 | 23.44 | 23.45 | 12.73 | 12.34 | 32.54 | 43.17 |
Under some fuel battery operation condition, the water-content of anode effluent is not enough to satisfy the needs of TSR or the demand that other system is reformed.Can add extra " replenishing " water (309) according to dotted line (305), yet in the preferred embodiment of the invention, selectable condenser and water receiver (311) are used for collecting and store from the next water of TSR regeneration effluent (308).When needed, this water can inject the circulation of TSR reformer with fuel (301) and anode effluent residual fuel (305).
Fig. 4 shows the embodiment of selecting of the present invention.When SOFC anode effluent does not contain enough fuel, thereby can not be when above-mentioned TSR regeneration effective supply, embodiment shown in the figure is favourable.In this embodiment, TSR reformer effluent (402) is divided into to the hydrogen-rich fuel gas (404) of SOFC anode supply and the sufficient fuel (403) of supplying to TSR regeneration.Anode waste gas (405) comprises remaining CO, CO
2, the water of generation and any residual fuel that is not consumed by SOFC, and be back to the material of reformer section as above-mentioned TSR reforming step.
Described similar to Fig. 3, oxygen-containing gas (406) is pressed the air supply usually, is provided to the negative electrode of SOFC.In preferred embodiments, negative electrode effluent (407) is used for the TSR regenerative process, introduces the oxygen demand that oxygen source of supply (406) is enough to supply the SOFC negative electrode that contains of negative electrode, and can be used as the oxygenant of TSR regeneration period.
Similar to Fig. 3 embodiment, selectable water condensing unit and water receiver (411) can be used for collecting and store from the next water of TSR regeneration effluent (408), and can be used for water (steam) demand of supply or additional TSR (409).
Fig. 5 shows the embodiment of selecting of the present invention, and it utilizes TSR fuel cell system shown in Figure 3, and with the combination of extra power generating device, normally turbine.With reference to the accompanying drawings, TSR (500) reforming step is supplied the logistics of hydrocarbonaceous (501) and steam (505); Reformation effluent (507) is supplied to SOFC (510) anode; The SOFC negative electrode is supplied air (506); Negative electrode effluent (502) is supplied to the TSR regeneration step; Be used for regenerated fuel (504) with SOFC anode effluent (503), above these all illustrate in Fig. 3.In this embodiment, the used heat from the TSR-SOFC system produces extra energy.Use SOFC used heat to produce steam (505).In one embodiment, as shown in Figure 5, in steam boiler (527,528), collect used heat respectively by cooling anodes and negative electrode effluent, thereby produce steam (505).In other embodiments (figure does not show), can directly collect heat from SOFC.Coupling compressor (515) and amplifier (516) advance air (514) compression in the negative electrode material (506), and are depressurized when becoming waste gas (517) at air, power from revivifier effluent (508) (518).The unnecessary steam of reforming outside required (505) can be added in the revivifier effluent (508), to increase booster output.
Claims (25)
1. method that produces electric energy comprises:
(a) in periodicity reformation and regenerative process, reforming has the hydrocarbon-bearing material of steam, comprising:
I. under the condition of reorganization, with 500hr at least
-1C
1The GHSV air speed, first district that introduces material and the steam reactor by containing a packing material and reforming catalyst, wherein C
1GHSV is based on C
1The air speed of hydrocarbon fuel;
Second district of the reactor of at least a portion product that ii. makes step I by containing a packing material, and heat is passed to described packing material from product;
Iii. remove all products basically from described second district, described product comprises hydrogen-rich synthetic gas;
Iv. oxygen-containing gas is introduced described second district, and make described gas and fuel with described first district and the contiguous location burning of the described second regional boundary face, producing heat and products of combustion, and the combustion heat is passed to a packing material in described first district,
V. remove all products of combustion basically from described first district.
(b) the described reformate with step I ii is supplied to the anode of solid-oxide fuel cell with power supply.
2. the method for claim 1 wherein comprises described periodicity reformation processing unit and described solid-oxide fuel cell jointly.
3. the method for claim 1, wherein said periodicity is reformed and reclaiming process has characteristic heat transfer Δ temperature, Δ T
HT, be 0.1 ℃～500 ℃, Δ T wherein
HTBe the average-volume rate of heat transfer H of bed and the volumetric heat transfer coefficient h of bed
vRatio.
4. method as claimed in claim 3, wherein Δ T
HTIt is 0.5 ℃～40 ℃.
5. the method for claim 1, wherein said air speed is 1,000～100,000hr
-1
6. method as claimed in claim 5, wherein said air speed are 2,000～50,000hr
-1
7. method as claimed in claim 5, the volumetric heat transfer coefficient of wherein said reactor beds packing material is more than or equal to 0.05cal/cm
3S ℃.
8. method as claimed in claim 7, wherein said packing material are cellular monoblock material, and its channel density is 15 passage/cm
2To 500 passage/cm
2
9. method as claimed in claim 5, the wetting areas of wherein said packing material is more than or equal to 6cm
-1
10. method as claimed in claim 5, the packing material in wherein said first district or described second district or these two districts is made by being selected from following material: stable or unsettled magnesium aluminum silicate, aluminum silicate clay, mullite, aluminum oxide, silica-alumina, zirconium white and its mixture.
11. the method for claim 1, wherein said catalyzer is selected from the precious metal composition.
12. the method for claim 1, wherein said catalyzer is selected from the group VIII metal ingredient.
13. the method for claim 1, wherein said catalyzer is selected from Ag, Ce, Cu, La, Mo, Mg, Sn, Ti, Y and Zn.
14. the method for claim 1, the wherein said temperature in that has the hydrocarbon-bearing material of steam is 20 ℃～1000 ℃.
15. method as claimed in claim 14, the wherein said temperature in that has the hydrocarbon-bearing material of steam is 200 ℃～600 ℃.
16. the method for claim 1, wherein said the condition of reorganization comprise that at least a portion of reforming catalyst is heated to 700 ℃～2000 ℃ temperature.
17. the method for claim 1, wherein fuel cell cathode flow goes out the step I v that thing is supplied to described fuel of at least a portion and oxygen-containing gas described method.
18. method as claimed in claim 17, wherein the anode of fuel cell effluent is with the step I of at least a portion steam supply to described method.
19. method as claimed in claim 17, wherein the negative electrode effluent is supplied to the location of being close to described first district and the second regional boundary face with the described oxygen-containing gas of at least a portion, is used for the step I v of described method.
20. method as claimed in claim 2, wherein the further feature of step (b) is under greater than 200 ℃ temperature, will contain hydrogen, CO, CO
2, hydrocarbon and steam reformate be supplied to described anode of fuel cell, thereby described reformate further reformed, and hydrogen-rich synthetic gas is supplied to the anode of described fuel cell.
21. the method for claim 1, the fuel among the wherein said method steps iv is supplied by at least a portion synthetic gas of described method steps iii.
22. the method for claim 1 comprises:
Measure at the interface or basically at the interface temperature of described first district and second district,, just described oxygen-containing gas is introduced described second district in case arrive predetermined first temperature; With
Measure described first district first end temperature on every side,, just described hydrocarbon-bearing material and steam material are introduced first end in described first district in case arrive predetermined second temperature.
23. the method for claim 1 comprises:
Measure described first district and second regional boundary face temperature on every side,, just begin regeneration step iv and measure described first district first end temperature on every side,, just begin reformation and recycling step i, ii and iii in case arrive the second predetermined temperature in case arrive preset temperature.
24. the method for claim 1, wherein operate two or more reactors simultaneously, make step I, ii and iii carry out at least one reactor, and step I v and v are carrying out in another reactor at least, thereby provide continual basically reformate stream to described fuel cell.
25. the method for claim 1, the effluent of wherein said regenerative process provides power with generating to turbine.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US47286403P | 2003-05-23 | 2003-05-23 | |
| US60/472,864 | 2003-05-23 | ||
| US10/848,095 | 2004-05-18 |
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| Publication Number | Publication Date |
|---|---|
| CN1795142A CN1795142A (en) | 2006-06-28 |
| CN100540459C true CN100540459C (en) | 2009-09-16 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021055186A1 (en) * | 2019-09-18 | 2021-03-25 | Exxonmobil Research And Engineering Company | Processes and systems for making synthesis gas |
| WO2021055185A1 (en) * | 2019-09-16 | 2021-03-25 | Exxonmobil Research And Engineering Company | Processes and systems for making synthesis gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017087188A1 (en) * | 2015-11-18 | 2017-05-26 | Exxonmobil Research And Engineering Company | Heat-resistant hydrocarbon reforming catalyst based on rhodium on a lanthanum-stabilised theta-alumina |
| NO345296B1 (en) * | 2016-07-14 | 2020-11-30 | Zeg Power As | Method and power plant comprising a Solid Oxide Fuel Cell (SOFC) for production of electrical energy and H2 gas |
| EP3308851A1 (en) * | 2016-10-17 | 2018-04-18 | ETH Zurich | A thermochemical reactor system for a temperature swing cyclic process with integrated heat recovery and a method for operating the same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021055185A1 (en) * | 2019-09-16 | 2021-03-25 | Exxonmobil Research And Engineering Company | Processes and systems for making synthesis gas |
| WO2021055186A1 (en) * | 2019-09-18 | 2021-03-25 | Exxonmobil Research And Engineering Company | Processes and systems for making synthesis gas |
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