CN104587912A - Fluidized bed reactor, fluidized bed reaction apparatus, and methane water-vapour reforming method - Google Patents
Fluidized bed reactor, fluidized bed reaction apparatus, and methane water-vapour reforming method Download PDFInfo
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- CN104587912A CN104587912A CN201310528652.8A CN201310528652A CN104587912A CN 104587912 A CN104587912 A CN 104587912A CN 201310528652 A CN201310528652 A CN 201310528652A CN 104587912 A CN104587912 A CN 104587912A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
- B01J8/26—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations
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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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/42—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts using moving solid particles
- C01B3/44—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts using moving solid particles using the fluidised bed technique
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Abstract
The invention provides a fluidized bed reactor. A reaction area of the reactor is provided with foam metal plates with catalytic activity, the foam metal plates are longitudinally and/or transversely arranged along the reaction area, the space among the foam metal plates and/or the space between the foam metal plates with the inner wall of the reaction area are/is used to hold a fluidizable particle, and the fluidizable particle can pass through pores on the transversely-arranged foam metal plates. The invention also provides a fluidized bed reaction apparatus which comprises the fluidized bed reactor and a regenerator. The invention also provides a methane water-vapour reforming method using the fluidized bed reaction apparatus, and the foam metal plates have catalytic activity on the methane water-vapour reforming reaction, and at least a part of the fluidizable particle has adsorption effect on carbon dioxide. In the method, the catalyst does not need frequently regenerating along with the adsorbent, when the adsorbent is guaranteed to be always capable of satisfying usage requirements, energy consumption during regeneration is reduced, and senseless reduction of the catalyst activity is avoided.
Description
Technical field
The present invention relates to a kind of fluidized-bed reactor, the invention still further relates to a kind of fluidized bed reaction using described fluidized-bed reactor, the invention further relates to a kind of methane steam reformation method.
Background technology
Along with the development of economic society, the demand for the energy increases gradually; But petroleum resources are day by day exhausted and environmental pollution is day by day serious, develop and utilize clean energy resource to become the focus of research.The calorific value that hydrogen not only burns is high, and due to combustion product be water, can not have a negative impact to environment, be a kind of efficiently desirable clean energy resource.
Methane (that is, natural gas) can prepare hydrogen by steam reformation, and the reserves of natural gas comparatively horn of plenty in world wide, therefore, develop and utilize Hydrogen Energy to come into one's own gradually.
Methane steam reformation is a reversible reaction, and its reaction equation is as follows:
For reversible reaction, carrying out being separated while reaction is one of effective way obtaining high feed stock conversion and target product yield.Therefore, adsorption forced methane steam reforming hydrogen manufacturing technology is arisen at the historic moment.
Adsorption forced methane steam reforming hydrogen manufacturing technology is on the basis of methane steam reformation reaction, by adding carbon dioxide absorber (being generally calcium oxide), by the carbon dioxide removing produced in reforming reaction process, thus break chemical reaction equilibrium, improve the conversion ratio of methane, obtain highly purified hydrogen.
At present, methane mainly contacts with the mixture of catalyst with carbonated adsorbent with water vapour by adsorption forced methane steam reforming hydrogen manufacturing technology, obtains hydrogen.Reaction temperature and reaction speed can be improved by adsorption forced methane steam reforming hydrogen manufacturing technology, obtain the hydrogen of high concentration.
Summary of the invention
The present inventor finds in research process, and existing adsorption forced methane steam reforming hydrogen manufacturing technology exists the fast problem of catalyst activity reduction.Through research, find that its main cause is: in adsorption forced methane steam reforming hydrogen manufacturing technology, carbon dioxide absorber needed to regenerate owing to reaching adsorption equilibrium in use a period of time, to recover adsorption activity, therefore need the mixture of carbon dioxide absorber and catalyst regularly to send in regeneration unit to regenerate; But frequent regeneration process adds the reduction process of catalyst, also make catalyst experienced by unnecessary high and low temperature shift simultaneously, and coated by Calcium compounds high temperature, thus cause catalyst activity reduction.
The object of the invention is to the above-mentioned technical problem overcoming the existence of existing methane steam reforming hydrogen manufacturing technology, a kind of new hydrogen production method from methane steam reformation is provided, this method avoid the activity decrease caused due to catalyst frequent regeneration.
According to a first aspect of the invention, the invention provides a kind of fluidized-bed reactor, this fluidized-bed reactor comprises the reactor body for hollow, the inner space of described reactor body comprises reaction zone, wherein, one or more foam metal plate with catalytic activity is provided with in described reaction zone, multiple described foam metal plate interval is arranged, described foam metal plate is along the longitudinal direction of described reaction zone and/or horizontally set, space between described foam metal plate and/or the space between described foam metal plate and the inwall of described reaction zone are used for accommodation can fluidized grain, hole on the described foam metal plate of horizontally set is enough to make described can passing through by fluidized grain.
According to a second aspect of the invention, the invention provides a kind of fluidized bed reaction, this fluidized bed reaction comprises fluidized-bed reactor and regenerator, described fluidized-bed reactor is fluidized-bed reactor provided by the invention, and described regenerator is for can regenerating by fluidized grain of the activity from described fluidized-bed reactor being reduced.
Load in the reaction region while fluidized grain, the foam metal plate with catalytic activity can be introduced according to fluidized-bed reactor of the present invention, described can fluidized grain be the particle with catalytic activity time, dual catalytic effect can be realized; Described can fluidized grain be the particle with other function of such as adsorbing time, can while carrying out reacting, realize such as removing the effect that the Small molecular produced in course of reaction improves the extent of reaction.
The more important thing is, according to fluidized-bed reactor of the present invention, can can fluidized grain by needing the component often carrying out regenerating to make, and the component without the need to frequent regeneration is made foam metal plate, the energy consumption of regeneration can not only be reduced, it also avoid by direct for two kinds of materials used in combination time, service life itself, longer catalyst was due to optionally frequent regeneration and the activity decrease caused.
According to a third aspect of the present invention, the invention provides a kind of methane steam reformation method, the method is carried out in fluidized bed reaction provided by the invention, described foam metal plate has catalytic activity to methane steam reformation reaction, described at least partly can have suction-operated to carbon dioxide by fluidized grain, the method comprises to be sent in described reaction zone by methane and water vapour, haptoreaction under methane steam reformation reaction condition; That is reduced by least part of adsorption activity can send in described regenerator and regenerates by fluidized grain, and by can send back in described fluidized-bed reactor by fluidized grain after regeneration at least partly.
Compared with existing adsorption forced methane steam reforming hydrogen manufacturing technology, catalyst is made foam metal plate or load on foam metal plate by method of the present invention dexterously, fix in the reactor, adsorbent is made and can regularly regenerate by fluidized grain, such catalyst need not carry out frequent regeneration with adsorbent, while guaranteeing that the suction-operated of adsorbent can meet instructions for use all the time, not only reduce energy consumption and the hydrogen consumption of regenerative process, and avoid the meaningless decline of catalyst activity.In addition, according to method of the present invention, catalyst is made foam metal plate or load on foam metal plate, there is higher catalytic activity.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with detailed description of the invention one below.In the accompanying drawings:
Fig. 1 is for illustration of a kind of embodiment of fluidized bed reaction according to the present invention.
Fig. 2 is for illustration of the another kind of embodiment of fluidized bed reaction according to the present invention.
Description of reference numerals
100: fluidized-bed reactor 101: reactor body
102: reaction zone 103: decanting zone
104: foam metal plate 105: can the space of fluidized grain for holding
106: cyclone separator 107: inactivation can fluidized grain efferent duct
108: regeneration can fluidized grain input pipe 109: material inlet
110: material outlet 111: feed distributor
200: regenerator 201: regenerating medium entrance
202: cyclone separator 203: regenerating medium exports
Detailed description of the invention
The invention provides a kind of fluidized-bed reactor, this fluidized-bed reactor comprises the reactor body for hollow, and the inner space of described reactor body comprises reaction zone.Described reaction zone refers to that reactant carries out the space of reacting.Described can fluidized grain refer to by streaming flow effect can space suspend get up particle.
Described reaction zone can be straight barrel type reaction zone, also can be reducing reaction zone, is preferably reducing reaction zone.When described reaction zone is reducing reaction zone, described reaction zone preferably includes direct tube section and extension diameter section.The outer contour of extension diameter section and the angle of horizontal plane can be conventional selection.Usually, the outer contour of extension diameter section and the angle of horizontal plane can be 30-75 °, are preferably 35-60 °.The cross section of described reaction zone can be circular or square.
One or more foam metal plate with catalytic activity is provided with in described reaction zone, described foam metal plate is along the longitudinal direction of described reaction zone and/or horizontally set, and the space between described foam metal plate and/or the space between the inwall of foam metal plate and described reaction zone are used for accommodation can fluidized grain.When described foam metal plate is multiple, multiple described foam metal plate is that interval is arranged.Interval between described foam metal plate is preferably identical.
The size of described foam metal plate is fixed with the size of reaction zone.Usually, the thickness of described foam metal plate can be 2mm-200mm, and being preferably 2mm-100mm, can be generally 2mm-10mm.
For the described foam metal plate longitudinally arranged, the ratio of the height of described foam metal plate and the height of described reaction zone can be 0.1-1:1, and the lower edge of described foam metal plate can be 0.01-0.5:1 to the minimum range of bottom of described reaction zone and the ratio of the height of described reaction zone.The upper edge of described foam metal plate can be concordant with the top of described reaction zone.Preferably, there is certain distance between the upper edge of described foam metal plate and the top of described reaction zone, particularly, the upper edge of described foam metal plate is 0.01-0.2:1 to the minimum range at top of described reaction zone and the ratio of the height of described reaction zone.The sidewall of described foam metal plate preferably connects with the inwall of described reaction zone.
For the described foam metal plate of horizontally set, the outer rim of described foam metal plate preferably connects with the inwall of described reaction zone; Undermost foam metal plate can be 0.01-0.5:1 to the distance of bottom of described reaction zone and the ratio of the height of described reaction zone.Described foam metal plate is preferably to be equidistantly evenly arranged in described reaction zone.
The shape of described foam metal plate can be selected according to the shape of reaction zone.Usually, the shape of the foam metal plate of horizontally set is identical with the shape of the horizontal cross-section of described reaction zone; The foam metal plate longitudinally arranged is preferably square.
Conventional method can be adopted to be arranged in the reaction region by described foam metal plate.Particularly, when described foam metal plate is longitudinally arranged in reaction zone, fixed pedestal can be set the corresponding position in reaction zone, the two ends of described foam metal plate are fixed on described fixed pedestal.When described foam metal plate is transversely arranged in reaction zone, the described outer rim of foam metal plate can be fixedly connected with the inwall of reactor, thus described foam metal plate is fixed in the reaction region.
The quantity of described foam metal plate can be selected according to the treating capacity of reactor and concrete reaction type, so that can either catalytic action be realized, and again can for enough spaces can be reserved be as the criterion by fluidized grain.Usually, the filling rate of described foam metal plate in described reaction zone can be 10-90 volume %.Described filling rate refers to that the volume of foam metal plate accounts for the percentage of the volume of reaction zone.
According to fluidized-bed reactor of the present invention, described foam metal plate has catalytic activity to the reaction carried out in the reaction region.Various method can be adopted to make described foam metal plate have catalytic activity.
In one embodiment of the invention, described foam metal plate can for be made up of the mixture containing catalytic active component.In this embodiment, described foam metal plate itself has catalytic activity.
In another embodiment of the invention, on described foam metal, load has catalytic active component.In this embodiment, foam metal plate originally as inactive, but carrys out supporting catalytic active composition as carrier.Described nonactive referring to does not have catalytic action to reaction, also can not with reactant and reaction product generation chemical interaction.Conventional various methods can be adopted using catalytic active component load as on the foam metal plate of carrier.Such as, can by flood and/or the method such as spraying by catalytic active component load on inactive foam metal plate.
The kind of described catalytic active component can be selected according to the particular type of the reaction carried out in the reaction region.Such as, when the reaction carried out in the reaction region is methane steam reformation reaction, described catalytic active component can be the component steam reforming reaction of methane to catalytic activity, such as: nickel catalyst.
Described foam metal plate refers to and foam metal is shaped to plate shape.Described foam metal plate has hole.For the foam metal plate of horizontally set, the size of described hole should be enough to make described can passing through by fluidized grain.Therefore, for the foam metal plate of horizontally set, the size of described hole with described can the size of fluidized grain and fixed.Usually, the average pore size of the hole on the described foam metal plate of horizontally set can be 1-50mm, is preferably below 20mm, is more preferably below 10mm, more preferably below 5mm (as below 2mm).For the described foam metal plate longitudinally arranged, the average pore size of described hole can be 10 μm to 10mm, be preferably 20 μm to 5mm, be more preferably 500 μm of-1.5mm, be conducive to the Homogeneous phase mixing of the material in reaction zone like this.
Usually, the porosity on described foam metal plate is more than 90%.Described porosity is the percentage that the volume of hole on foam metal plate accounts for the cumulative volume of foam metal plate.Described porosity can adopt water seaoning to measure, namely, respectively the foam metal plate of same volume and non-foam metallic plate are immersed in water, the difference of the volume of the water that both mensuration is discharged, using the difference of volume of water of discharging and the percent value of the volume of non-foam metal as the porosity of foam metal plate.
Described foam metal plate can be commercially available, the method preparation that this area also can be adopted conventional, such as: can by containing blowing agent (as NH
4cl) raw mixture carries out sintering and obtaining.
Describedly can to select according to concrete reaction type by fluidized grain, can catalytic activity be had, also can have other effect except catalytic activity.
Such as, when the reaction needed of carrying out in the reaction region uses dual-component catalyst system, described at least partly can fluidized grain can be the another kind of component reaction carried out in the reaction region to catalytic activity.Now, particularly preferably the component that relatively short for the life-span in dual-component catalyst system needs often carry out regenerating being made can fluidized grain, and the component relatively grown in the life-span makes foam metal plate, can effectively avoid two kinds of components all to make like this can fluidized grain time, the component relatively grown of life-span carries out the deficiency of unnecessary regeneration.
Again such as, at least partly described can fluidized grain can for having adsorbing adsorbent, particularly, when the reaction carried out in the reaction region is the reversible reaction generating small-molecule substance, described can have suction-operated to the small-molecule substance generated in course of reaction by fluidized grain, can carry out in the process of reacting, the Small molecular generated in course of reaction being removed from reaction system like this, promote that reaction is carried out to positive direction, and then improve the conversion ratio of raw material and the productive rate of product.Simultaneously, due to can fluidized grain reach adsorption equilibrium time, can only using can regenerate in fluidized grain feeding regeneration unit as adsorbent, and need not as catalyst and adsorbent are all made can fluidized grain time, need catalyst and adsorbent to regenerate simultaneously, not only alleviate the burden of regeneration unit, reduce energy consumption; And avoid the activity decrease that catalyst causes due to frequent regeneration.
Described can the particle diameter of fluidized grain can fluidization be as the criterion.Usually, describedly the average grain diameter of fluidized grain can be able to be 20 μm-120 μm, be preferably 40 μm-100 μm.Described average grain diameter is the volume average particle size adopting laser particle size analyzer to measure.
In a kind of embodiment of fluidized-bed reactor of the present invention, described foam metal plate has catalytic activity to methane steam reformation reaction, and described at least partly can have suction-operated to carbon dioxide by fluidized grain, as calcium oxide particle.According to this embodiment, can methane and water vapour carried out in the process of reforming reaction, the carbon dioxide that reaction generates is being removed, impel reaction to carry out to positive direction, improve the degree of reaction; , when adsorbent reaches adsorption equilibrium, only can regenerate by fluidized grain meanwhile, and without the need to catalyst is regenerated.According to this embodiment, can fluidized grain can be all calcium oxide particle although described, but, preferably, described can fluidized grain be the composite particles of calcium oxide and aluminium oxide, such one side can improve can the mechanical strength of fluidized grain, on the other hand can the bulk density of fluidized grain by regulating the ratio between calcium oxide and aluminium oxide adjust.More preferably, with described can the total amount of fluidized grain for benchmark, the content of described calcium oxide can be 20-99 % by weight, and the content of described aluminium oxide can be 1-80 % by weight.Described composite particles can obtain by calcium oxide to be mixed rear granulation with aluminium oxide.
According to fluidized-bed reactor of the present invention, in a preferred embodiment, the inner space of described reactor body also comprises decanting zone, described decanting zone is positioned at the top of described reaction zone, for receive the reactant mixture that comes from described reaction zone and make to carry secretly in described reaction-ure mixture can return described reaction zone by fluidized grain at least partly.
The shape of described decanting zone can be that the routine of this area is selected, can fluidized grain sedimentation return reaction zone and be as the criterion with what can realize making granularity larger.Usually, described decanting zone is tubular.The cross sectional shape of described decanting zone can be circular or square.
Ratio between described decanting zone and described reaction zone can be conventional selection, is not particularly limited.
In a kind of further preferred embodiment of the present invention, described fluidized-bed reactor also comprises the solid particle separator be arranged in described decanting zone, described solid particle separator is used for isolating from described reactant mixture can fluidized grain, and can send back in described reaction zone by fluidized grain by isolated, the reactant mixture of fluidized grain can send described fluidized-bed reactor by isolating.Described particle separator can be the conventional various separators can isolating solid particle, as cyclone separator.Described particle separator can be one or more, when described particle separator is multiple, is preferably connected in series by multiple particle separator, can obtains better separating effect like this.
Also comprise at least one material inlet and at least one material outlet according to fluidized-bed reactor of the present invention, described material inlet is positioned at the bottom (bottom as reaction zone) of described reaction zone, reacts for being sent in reaction zone by reaction raw materials; Described material outlet is positioned at the top (top as reactor) of described reaction zone, sends reactor for mixture reaction generated.Described fluidized-bed reactor can also comprise the feed distributor be arranged near material inlet, for the charging uniform distribution that will enter through material inlet in reaction zone.
According to fluidized-bed reactor of the present invention preferably also comprise for activity is reduced can fluidized grain export to regeneration unit inactivation can fluidized grain efferent duct and be used for by regeneration can fluidized grain send into the regeneration of reaction zone can fluidized grain input pipe.Described inactivation can generally can be arranged in the upper portion side wall of reaction zone of reactor body by fluidized grain efferent duct, and described regeneration can be arranged on the lower sides of described reactor body by fluidized grain input pipe.
Fluidized-bed reactor according to the present invention is particularly suitable for the reactor as the reaction using dual-component catalyst system, or as the reactor needed removing micromolecular reaction (as: reversible reaction with small-molecule substance generates) in course of reaction.
Present invention also offers a kind of fluidized bed reaction, comprise fluidized-bed reactor of the present invention and regenerator, described regenerator is for can regenerating by fluidized grain of the activity coming from described fluidized-bed reactor being reduced.
Described fluidized-bed reactor and structure thereof are described above, no longer describe in detail herein.
Described regenerator can according to can the kind of fluidized grain and renovation process select.Usually, described regenerator can comprise the seal casinghousing for hollow structure, described seal casinghousing is provided with can the spent agent entrance of fluidized grain for what receive that the activity that comes from described fluidized-bed reactor reduces, can the regenerative agent outlet of fluidized grain for what export regeneration, be respectively used to pass into and derive regenerating medium entrance and the regenerating medium outlet of regenerating medium.The inner space of described seal casinghousing can as the regenerative space carrying out regenerating.The mode of described regeneration can be roasting or washing.The kind of described regenerating medium can be selected according to regeneration.
Fig. 1 shows a kind of embodiment according to fluidized bed reaction of the present invention.As shown in Figure 1, this fluidized bed reaction comprises fluidized-bed reactor 100 and regenerator 200.
As shown in Figure 1, the inner space of the reactor body 101 of fluidized-bed reactor 100 comprises reaction zone 102 and decanting zone 103 from bottom to top; Be vertically arranged with foam metal plate 104 in reaction zone 102, the side of foam metal plate 104 connects with the inwall of reaction zone 102; Space 105 between the inwall of the space between foam metal plate 104 and foam metal plate 104 and reaction zone 102 is can the space of fluidized grain for holding; Cyclone separator 106 is provided with in decanting zone 103.
As shown in Figure 1, the upper portion side wall of fluidized-bed reactor 100 is provided with for export to be generated can the inactivation of fluidized grain can fluidized grain efferent duct 107, the lower sides of fluidized-bed reactor 100 is provided with for input regeneration can the inactivation of fluidized grain can fluidized grain input pipe 108, wherein, inactivation can be communicated with the spent agent entrance of regenerator 200 by fluidized grain efferent duct 107, and inactivation can the regenerative agent outlet of fluidized grain input pipe 108 and regenerator 200.
When operating, can be seated in space 105 by fluidized grain, reaction mass be by the material inlet 109 being arranged in fluidized-bed bottom and enter reaction zone 102 through feed distributor 111 and react.The reactant mixture obtained by reaction zone 102 upwards enters in decanting zone 103.In decanting zone 103, the solid particles sediment that in reactant mixture, particle is larger returns in reaction zone 102, remaining reactant mixture enters in cyclone separator 106, further be separated, isolated solid particle is returned in reaction zone 102 by the material pin of cyclone separator 106, and the logistics having isolated solid particle then exports to enter in follow-up unit by the material outlet 110 arranging fluidized-bed reactor 100 top carries out separation and purification.In course of reaction, that activity is reduced by efferent duct 107 can be regenerated in fluidized grain feeding regenerator 200.In regenerator 200, regenerating medium enters in the regenerative space of regenerator by the regenerating medium entrance 201 be arranged on bottom regenerator 200, can contact by fluidized grain with to be generated, with make to be generated can fluidized grain activity recovery.The regenerative agent obtained is exported and is understood by input pipe 108 circulation in the reaction zone 102 of fluidized-bed reactor 100 from regenerator.After solid particle wherein being isolated by the cyclone separator 202 of regenerating medium through being arranged on regenerative space top that regenerative space exports, exporting 203 by regenerating medium and exporting.
Fig. 2 shows the another kind of embodiment according to fluidized bed reaction of the present invention.The difference of this embodiment and Fig. 1 illustrated embodiment is: foam metal plate 104 is horizontally installed in reaction zone 103 along reaction zone 102, wherein, the outer rim of foam metal plate 104 connects with the inwall of reaction zone 102, and the hole on foam metal plate 104 is enough to make to pass through by fluidized grain.
Fluidized bed reaction of the present invention is suitable for the reactor of the reversible reaction as the micromolecular compound generated in course of reaction, as the steam reforming reaction of methane.
Thus, invention further provides a kind of methane steam reformation method, the method is carried out in fluidized bed reaction provided by the invention, wherein, described foam metal plate has catalytic activity to methane steam reformation reaction, described at least partly can have suction-operated to carbon dioxide by fluidized grain, and the method comprises to be sent in described reaction zone by methane and water vapour, haptoreaction under methane steam reformation reaction condition; That is reduced by least part of adsorption activity can send in described regenerator and regenerates by fluidized grain, and by can send back in described fluidized-bed reactor by fluidized grain after regeneration at least partly.
Described fluidized bed reaction and structure thereof are described above, repeat no more herein.
According to method of the present invention, can by make described foam metal plate have to methane steam reformation reaction have catalytic action component and make described foam metal plate have catalytic activity.
Component methane steam reformation reaction to catalytic action can be various to methane steam reformation catalysts for what commonly use, such as: nickel catalyst, platinum group catalyst and palladium series catalyst, are preferably nickel catalyst.Nickel catalyst is generally containing as the nickel of host and auxiliary agent, and in the total amount of catalyst for benchmark and with element, the content of described host can be 5-99.9 % by weight, preferably 70-95 % by weight; The content of described auxiliary agent can be 0.1-95 % by weight, is preferably 5-30 % by weight.Described auxiliary agent can be one or more in tungsten, iron, chromium, aluminium oxide and zirconia.
Can described foam metal plate be formed with containing mixture methane steam reformation reaction to the component of catalytic action thus make described foam metal plate have catalytic activity.Particularly, component and blowing agent (e.g., the NH methane steam reformation reaction to catalytic action will can be contained
4cl) mix, and sinter, thus obtain foam metal plate methane steam reformation reaction to catalytic action.
Also can be that on inactive foam metal plate, the component with catalytic action is reacted in load to methane steam reformation, namely, using inactive foam metal plate as carrier to methane steam reformation reaction.The load on inactive foam metal plate of conventional various methods can be adopted to have the component of catalytic action to methane steam reformation reaction, such as: can by flood and/or the method such as spraying has the component load of catalytic action on inactive foam metal plate by methane steam reformation reaction.Described nonactive foam metal plate can be common various be the foam metal plate that inactive metal is formed at reaction conditions, such as: the foam metal plate formed by one or more in copper, chromium, silver and iron.
The content of the catalytic active component in described foam metal plate is as the criterion can realize catalysis, can select, be not particularly limited according to the treating capacity of device.
According to method of the present invention, to carbon dioxide have adsorbing can fluidized grain can for various can the solid particle of absorbing carbon dioxide, such as: calcium oxide particle and/or magnesium oxide particle, be preferably calcium oxide particle.
According to method of the present invention, can the angle of mechanical strength of fluidized grain from improving further, describedly can be preferably the composite particles of calcium oxide and aluminium oxide by fluidized grain.In described composite particles, the content of calcium oxide is as the criterion can realize adsorption function.Preferably, with described can the total amount of fluidized grain for benchmark, the content of described calcium oxide can be 20-99 % by weight, and the content of described aluminium oxide can be 1-80 % by weight.Described composite particles can obtain by calcium oxide to be mixed rear granulation with aluminium oxide.
The condition of described regeneration can according to can the kind of fluidized grain select.Usually, that activity can be reduced can carry out roasting by fluidized grain at the temperature of 500-950 DEG C, thus make can fluidized grain activity recovery.The time of described roasting can be selected according to the temperature of roasting, can be generally 750-900 DEG C.Described roasting is generally carried out in nitrogen or air atmosphere.
According to method of the present invention, the ratio of methane and water vapour can be conventional selection.Usually, the mol ratio of methane and water vapour can be 0.2-1:1, is preferably 0.25-1:1.
Described methane steam reformation reaction condition can be conventional selection.Usually, temperature can be 500-750 DEG C, is preferably 520-700 DEG C; In gauge pressure, pressure can be 0.01-3.5MPa, is preferably 0.1-3MPa; During gas, volume space velocity can be 10-1500h
-1, be preferably 20-1000h
-1.During described gas, volume space velocity is charging (with methanometer) relative to can the air speed of fluidized grain.
The present invention is described in detail below in conjunction with embodiment.
In following examples and comparative example, the composition of the reactant mixture adopting gas chromatography determination fluidized-bed reactor to export.
In following examples, adopt the section of Electronic Speculum to foam metal plate observe thus determine the pore-size on foam metal plate, adopt water seaoning to measure the porosity of foam metal plate.
In following examples and comparative example, adopt and be purchased that measure from the laser particle size analyzer of Malvern company can the volume average particle size of fluidized grain.
Embodiment 1-2 is for illustration of the present invention.
Embodiment 1
The present embodiment adopts the fluidized bed reaction shown in Fig. 1, wherein:
(1) reaction zone of fluidized-bed reactor is that internal diameter is 160mm and is highly the cylinder of 1200mm, and the outer contour in expanding district and the angle of horizontal plane are 60 °, and decanting zone is that internal diameter is 240mm and is highly the cylinder of 400mm;
(2) 20 the foam metal plates that have longitudinally been equidistantly spaced in reaction zone (are produced by Beijing Zhong Shiqiangye foam metal Co., Ltd, foam metal plate is formed by nickel and tungsten, wherein, the weight ratio of nickel and tungsten is 1:0.1, the thickness of foam metal plate is 2mm, the average pore size of the hole on foam metal plate is 1mm, the porosity of foam metal plate is 95 volume %), the ratio of the minimum range at the upper surface of foam metal plate and the top of reaction zone and the height of reaction zone is 0.1:1, the minimum range of lower surface to the bottom of reaction zone of foam metal plate and the ratio of the height of reaction zone are 0.1:1, the sidewall of foam metal plate connects with the inwall of reaction zone,
(3) filling between foam metal plate and between foam metal plate and the inwall of reaction zone can fluidized grain, and described can fluidized grain be calcium oxide particle, and its volume average particle size is 70 μm.
Adopt following methods that methane is carried out steam reformation and obtain hydrogen:
By methane and water vapour with the mol ratio of 1:4 to send in fluidized-bed reactor under methane steam reformation reaction condition with foam metal plate and can fluidized grain haptoreaction.Wherein, the volume space velocity during gas of charging (with methanometer) (relative to can fluidized grain) is 750h
-1, the temperature in reaction zone is 600 DEG C; In gauge pressure, pressure is 0.3MPa.
In course of reaction, part can be regenerated in fluidized grain feeding regenerator, regeneration condition comprises: temperature is 800 DEG C, and the time is 0.5 hour, and regenerating medium is nitrogen.
Carry out the reaction of 16 hours continuously.Detected the composition of the reactant mixture exported from fluidized-bed reactor in course of reaction every 4 hours, calculate the conversion ratio of methane and the productive rate of hydrogen, result is listed in Table 1.
Comparative example 1
Adopt the method hydrogen making identical with embodiment 1, unlike, in reaction zone, foam metal plate is not set, the nickel catalyst identical with embodiment 1 is shaped to the spheric granules that volume average particle size is 70 μm, loads in the reaction region with the weight ratio of 0.5:1 with calcium oxide particle.
Carry out the reaction of 16 hours continuously.Detected the composition of the reactant mixture exported from fluidized-bed reactor in course of reaction every 4 hours, calculate the conversion ratio of methane and the productive rate of hydrogen, result is listed in Table 1.
Embodiment 2
Adopt the method hydrogen making identical with embodiment 1, unlike:
(1) in reaction zone, transversely equidistant uniform intervals is provided with 20 foam metal plates and (is produced by Beijing Zhong Shiqiangye foam metal Co., Ltd, for the nonactive foam metal plate formed by copper, on this nonactive foam metal plate, load has nickel and tungsten, wherein, the load capacity of nickel is 10 % by weight, the weight ratio of nickel and tungsten is 1:0.2, the thickness of this nonactive foam metal plate is 5mm, the average pore size of the hole on this nonactive foam metal plate is 2mm, porosity is 95%), the sidewall of foam metal plate connects with the inwall of reaction zone;
(2) filling between foam metal plate and between foam metal plate and the inwall of reaction zone can fluidized grain, and described can fluidized grain be calcium oxide particle, and its volume average particle size is 70 μm.
Adopt following methods that methane is carried out steam reformation and obtain hydrogen:
By methane and water vapour with the mol ratio of 1:4 to send in fluidized-bed reactor under methane steam reformation reaction condition with foam metal plate and can fluidized grain haptoreaction.Wherein, during the gas of charging (with methanometer, relative to can fluidized grain), volume space velocity is 1000h
-1, the temperature in reaction zone is 700 DEG C; In gauge pressure, pressure is 0.6MPa.
In course of reaction, part can be regenerated in fluidized grain feeding regenerator, regeneration condition comprises: temperature is 800 DEG C, and the time is 0.5 hour, and regenerating medium is nitrogen.
Carry out the reaction of 16 hours continuously.Detected the composition of the reactant mixture exported from fluidized-bed reactor in course of reaction every 4 hours, calculate the conversion ratio of methane and the productive rate of hydrogen, result is listed in Table 1.
Table 1
From the results shown in Table 1, adopt method of the present invention that methane is carried out steam reforming reaction, in continuous operation process, the long service life of catalyst, and the conversion ratio of stable methane and the productive rate of hydrogen can be obtained.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (14)
1. a fluidized-bed reactor, this fluidized-bed reactor comprises the reactor body for hollow, the inner space of described reactor body comprises reaction zone, it is characterized in that, one or more foam metal plate with catalytic activity is provided with in described reaction zone, multiple described foam metal plate interval is arranged, described foam metal plate is along the longitudinal direction of described reaction zone and/or horizontally set, space between described foam metal plate and/or the space between described foam metal plate and the inwall of described reaction zone are used for accommodation can fluidized grain, hole on the described foam metal plate of horizontally set is enough to make described can passing through by fluidized grain.
2. fluidized-bed reactor according to claim 1, wherein, the porosity of described foam metal plate is more than 90%.
3. fluidized-bed reactor according to claim 1, wherein, the inner space of described reactor body also comprises decanting zone, described decanting zone is positioned at the top of described reaction zone, for receive the reactant mixture that comes from described reaction zone and make to carry secretly in described reaction-ure mixture can return described reaction zone by fluidized grain at least partly.
4. fluidized-bed reactor according to claim 3, wherein, this fluidized-bed reactor also comprises the solid particle separator be arranged in described decanting zone, described solid particle separator is used for isolating from described reactant mixture can fluidized grain, and can send back in described reaction zone by fluidized grain by isolated, the reactant mixture of fluidized grain can send described fluidized-bed reactor by isolating.
5. according to the fluidized-bed reactor in claim 1,3 and 4 described in any one, wherein, described at least partly can fluidized grain be adsorbent.
6. fluidized-bed reactor according to claim 5, wherein, at least partly described can fluidized grain for there is adsorbing adsorbent to carbon dioxide.
7. fluidized-bed reactor according to claim 6, wherein, described foam metal plate has catalytic activity to methane steam reformation reaction.
8. a fluidized bed reaction, this fluidized bed reaction comprises fluidized-bed reactor and regenerator, described fluidized-bed reactor is the fluidized-bed reactor in claim 1-7 described in any one, and described regenerator is for can regenerating by fluidized grain of the activity from described fluidized-bed reactor being reduced.
9. a methane steam reformation method, the method is carried out in fluidized bed reaction according to claim 8, described foam metal plate has catalytic activity to methane steam reformation reaction, described at least partly can have suction-operated to carbon dioxide by fluidized grain, the method comprises to be sent in described reaction zone by methane and water vapour, haptoreaction under methane steam reformation reaction condition; That is reduced by least part of adsorption activity can send in described regenerator and regenerates by fluidized grain, and by can send back in described fluidized-bed reactor by fluidized grain after regeneration at least partly.
10. method according to claim 9, wherein, described foam metal plate is formed by containing reacting the mixture with the component of catalytic action to methane steam reformation, or on described foam metal plate, load has component methane steam reformation reaction to catalytic action.
11. methods according to claim 10, wherein, the described component having a catalytic action to methane steam reformation reaction is nickel system methane steam reformation catalyst.
12. methods according to claim 11, wherein, described nickel system methane steam reformation catalyst comprises nickel as host and auxiliary agent, in the total amount of catalyst for benchmark and with element, the content of described host is 5-99.9 % by weight, the content of described auxiliary agent is 0.1-95 % by weight, and described auxiliary agent is one or more in iron, tungsten, aluminium oxide and zirconia.
13. methods according to claim 9, wherein, having adsorbing to carbon dioxide can fluidized grain be calcium oxide particle.
14. methods according to claim 9, wherein, the mol ratio of described methane and described steam is 0.2-1:1, and described methane steam reformation reaction condition comprises: temperature is 500-750 DEG C; In gauge pressure, pressure is 0.01-3.5MPa; And volume space velocity is 10-1500h during gas
-1.
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