CN106929728A

CN106929728A - For the vanadium alloy of catalytic film reactor

Info

Publication number: CN106929728A
Application number: CN201511021441.0A
Authority: CN
Inventors: D·D·梁; M·D·多兰
Original assignee: Commonwealth Scientific and Industrial Research Organization CSIRO
Current assignee: Commonwealth Scientific and Industrial Research Organization CSIRO
Priority date: 2015-12-30
Filing date: 2015-12-30
Publication date: 2017-07-07

Abstract

The present invention relates to a kind of vanadium alloy and its production method for catalytic film reactor, and a kind of method for operating catalytic film reactor, the vanadium alloy is included：Vanadium；Content is the aluminium more than 0~10at%；Ta with content less than 0.01at%.

Description

For the vanadium alloy of catalytic film reactor

Technical field

Film this patent disclosure relates generally to the alloy for being used for membrane reactor, the film that is formed by the alloy and comprising the film is anti- Answer device and the method for operating the catalytic film reactor comprising the film formed by the alloy.The present invention is especially fitted For separating hydrogen from air-flow, such as in water transformationreation produce air-flow, and it is expedient to below for The exemplary application discloses the present invention.It should be appreciated, however, that the invention is not restricted to the application, and can have and need selection Property hydrogen separate or absorb wider application.

Background technology

Description to background of the present invention below is intended to promote the understanding of the present invention.It should be understood, however, that this description is not Recognize or approve mentioned any data be disclosed in the preference day of the application, it is known or for general knowledge one Point.

CO is captured from coal class energy system₂Discharge is a kind of greenhouse gases intensity that can be reduced in coal utilization Means.Capture can be carried out before combustion or after burning, wherein the energy matter of the synthesis gas from coal becomes via water-gas Change (WGS) reaction and be transformed to H₂, then carry out CO₂Separation and capture, as shown in (1)：

It is currently being deployed and H is isolated from mixed airflow₂The isolation technics based on film.In general, film is right A kind of species selectively can be saturating nearly two-dimensional structure.Under the background that gas is separate, film allows a kind of species selectively may be used (typically H thoroughly₂), while stopping other species (such as CO, CO₂、H₂O、N₂Deng).Hydrogen selective membrane can be by nothing Machine, metal or ceramic material are formed, and it each has hydrogen flux, operation temperature and the selectivity of characteristic.

Catalytic film reactor (CMR) incorporates hydrogen selective membrane and water gas converting catalyst such that it is able to produces and divides From H₂.The general rapid kineticses for being beneficial to WGS reactions in about 450 DEG C of operations of CMR.Additionally, CMR is allowed The conversion more than balance is realized, because through the H of film₂The lasting consumption of product pushes WGS reactions to product side. H₂Original position continuous extract the CO conversions for being capable of achieving almost 100%.

Palladium is known optimal alloy film material, and it has the hydrogen of 300 DEG C~600 DEG C of infiltration while keeping out such as CO And H₂The ability of the synthesis gas species such as O.However, high cost (the about $ US 330/m of palladium²/ μm (2014)) order about research Carried out towards following direction：Its consumption is minimized, most notably alloying is carried out by with more cheap metal, And by the deposit very thin in the supporting construction with superfine hole (<5 μm) layer its thickness minimized.

Many other metals present hydrogen transmissibility very high, most notably vanadium, titanium, tantalum and zirconium. At 400 DEG C, the hydrogen transmissibility of these metals is larger about two magnitudes than palladium, and cost of material is considerably lower.

In these metals, V has alloying scope most wide, it means that it has alloy characteristic is modified with full The widest range of sufficient CMR requirements.However, vanadium shows poor mechanical stability in the presence of the hydrogen, make it not Suitable for industrial hydrogen separating technology.Vanadium is easy to absorb the hydrogen of high concentration.Therefore, Vanadium hydride easily occur fragility break Bad, reason is that hydrogen has negative effect to the metallic bond in alloy.

For the H in CMR₂Any material of selective membrane must also have suitable formability/mechanical property, this Enable that the material is made into required configuration, such as flat or tubular film.For example, the conjunction for manufacturing tubular products Gold in production in enormous quantities generally show 25%~35% maximum elongation rate (by extrusion and drawing), and according to The deformation processing (the wherein deformation of every time (pass) is reduced, and has substantial amounts of calcining between passage) of customization, then maximum is stretched Rate long is at least 10%~20%.

United States Patent (USP) 7,001,446B2 discloses the hydrogen permeable membrane for separating hydrogen from hydrogen-containing gas.The film be with The multilayer of central hydrogen permeable layer and one or more catalyst layers, barrier layer and/or protective layer.In some embodiment party Central hydrogen permeable layer is taught in formula can metal or metal alloy thoroughly, including vanadium alloy comprising hydrogen.According to general teachings, greatly Measure suitable alloy and be suitable for this hydrogen permeable layer, such as those summarized in the table 1 of this United States Patent (USP).However, note Anticipate to without specific alloy according to teaching can provide be used as film, be more specifically be suitable to the optkmal characteristics of the tubular film of CMR.

Accordingly, it is desired to provide a kind of alloy and the film formed with the alloy, it has for CMR, is preferably used as The appropriate hydrogen conveying of the tubular film of CMR, mechanical stability and formability.

The content of the invention

The first aspect of the present invention provides a kind of vanadium alloy, and it includes：

Vanadium；

Content is the aluminium more than 0~10at%；With

Ta of the content less than 0.01at%.

During the alloy of first aspect present invention can be specifically for catalytic film reactor, particularly for catalytic film reactor Tubular film.

Present inventor have determined that vanadium class alloy should show following key characteristic to be most preferably used as in CMR reactors Alloy film：

- good diffusivity/absorptance, wherein, H high can be realized while hydrogen embrittlement effect is minimized₂ Permeability；

- good formability, including good ductility (ductility) (at least 10% elongation), it is allowed to preferably make The desired configuration of alloy film is manufactured with existing or known manufacturing process；With

- mechanical stability, in particular, α to β hydrogenation phase transitions is suppressed to shut down temperature in required CMR Degree left and right is following.This can allow the selected alloy can be in selected operation temperature (such as 400 DEG C) and (lower ) circulate between shutdown temperature (such as environment temperature), and do not suffer from the phase transformation of potential calamity.

Applicant carried out substantial amounts of tentative trial determining the V alloy (being described in detail below) being best suitable for.Research Many alloys, including V-Al, V-Ni, V-Cr and V-Ti-Al class alloy.V-Al class alloys are accredited as to be had Manufacture mechanical property of the pipe needed for (such as by tube-drawing, rolling or extrusion), and V-Ni and V-Cr alloys for It is excessively crisp for this manufacturing process.With reference to favourable Penetration Signature, V-Al alloys are have selected, reason is that it has completely The unexpectedly good and optimal characteristic of standard is enough to, particularly compared with other V alloys studied.

Alloy of the invention is vanadium class alloy.In some embodiments, content of vanadium is 85at%~98at%, preferably It is 90at%~96at%, preferably 91at%~96at%, more preferably 90at%~95at%.In some implementations In mode, content of vanadium is 92at%~98at%, preferably preferably 92at%~96at%, 92at%~97at%.

The main accessory ingredient of alloy of the invention is aluminium.Aluminium content ensure that alloy includes the vanadium with body-centered cubic structure Solid solution.And, the inventors discovered that, with the increase of Al content, the absorption of hydrogen is reduced, right so as to improve The resistance of hydrogen embrittlement.Note be also in the case of Ni and Cr in this way, but Ti be not.However, such as referenced below , selection aluminium is also based on assigning other advantageous features relevant with mechanical property and mechanical stability, including α-hydrogenation Thing and β-hydrogenation phase transition.The aluminium content of alloy is from more than 0 to 10at%.In some embodiments, aluminium Content is 0.1at%~9at%, preferably 0.5at%~8.5at%, preferably 1at%~10at%, more preferably 2 At%~8at%, still more preferably 3at%~7at%.In other embodiments, aluminium content is 1at%~10at%, Preferably 3at%~10at%, more preferably 2at%~6at%.

Further investigations have shown that addition grain refiner (such as titanium (Ti) and boron (B)) further improves the expectation of alloy Characteristic.Therefore, in certain embodiments of the present invention, vanadium alloy is from more than 0 to 5at% also comprising content Selected from the grain refining element of at least one of titanium (Ti), chromium (Cr), iron (Fe), nickel (Ni) and boron (B).Therefore, originally The alloy of invention selection includes vanadium class alloy, its following solid solution formula of tool：

V_100-(Y+Z)Al_YX_Z

At least one wherein in X=Ti, Cr, Fe, Ni or B；Y is>0~10；And Z is 0~5.

The inventor has discovered that Ti, Cr, Fe, Ni or B of addition serve as the grain refiner of vanadium solid solution (VSS). Grain form is preferably changed into dendroid by grain refiner from granular (having the crystallite dimension of several millimeters) (to be had and is less than 200 microns of a spacing).Preferably, grain refiner is Ti or B.

The formability of the reduction influence product of crystallite dimension, the extension of the product or other elements that are particularly formed by alloy Property.The maximum elongation rate of alloy is preferably greater than 10%, preferably greater than 11%, more preferably greater than 15%, so as to provide As the formability needed for film.The inventor has discovered that Al, Cr, the Ni of addition content more than 2at% all reduce vanadium Ductility.However, compared to other elements, the effect of Al is much smaller.The amount of grain refining element in alloy It is from more than 0 to 5at%, preferably 0.2at%~4at%, preferably from more than 0 to 2at%.In some implementations In mode, the content of grain refining element is 0.1at%~2at%, preferably 0.1at%~2at%, preferably 0.2 At%~1.5at%, more preferably 0.1at%~1at%.

Tantalum (Ta) content of alloy is preferably smaller than 0.01at%.The Ta for being preferable to minimize that and more preferably eliminating in alloy contains Amount, because tantalum content higher improves the rigidity of alloy, thus limits with the elongation achieved by the alloy. In some embodiments, tantalum (Ta) content of alloy is preferably smaller than 0.01at% but more than 0.

Importantly, alloy mechanically stable in the operating temperature range of film (particularly for the film of CMR).For Pure V, (has the body of gap hydrogen by α-hydride (having the body center cubic solid solution of the vanadium of gap hydrogen) and β-hydride The heart four directions solid solution) transformation occur at about 190 DEG C.This kind of phase in version causes stress in alloy, causes rupture.This Inventor is it has been found that addition Ni and Cr improves the critical transition temperature (T of hydride formation_C).Advantageously, originally Inventor also found that addition Al reduces transition temperature.For example, the Al of addition 10at% to be down to transition temperature small In 30 DEG C.The component (such as film) that this permission is formed by the alloy can under a hydrogen atmosphere experience thermal cycle.In the feelings of film Under condition, in high temperature (such as 400 DEG C) and low temperature (such as environment temperature) during the film being made in the startup of CMR and being shut down Between carry out thermal cycle, and do not suffer from being likely to result in the phase in version of rupture.In some embodiments, it may be preferable that closing The composition of gold causes that the phase transition temperature between the α-hydride phase and β-hydride phase of vanadium alloy is less than 100 DEG C, preferably Less than 50 DEG C, more preferably less than 30 DEG C, even more preferably less than 20 DEG C.

The vanadium of business form contains the dissolved oxygen of the level of signifiance.Oxygen is reacted by the hydrogen with dissolving can cause embrittlement.However, The inventors discovered that Al and Ti removes oxygen from vanadium.It is therefore preferable that providing comprising the conjunction for reducing alloy oxygen content The alloy of aurification component.The oxygen content of alloy is preferably smaller than 0.15wt%, preferably smaller than 0.1wt%, preferably smaller than 0.8 Wt%, more preferably less than 0.05wt%.

It should be appreciated that vanadium alloy can include impurity component, although typically less impurity component.In the side of being preferable to carry out In formula, impurity content is less than 0.5at%, more preferably less than preferably smaller than 0.1at%, 0.05at%.

Alloy of the invention can be manufactured by any suitable method.In a preferred form, alloy includes the alloy of casting.

The second aspect of the present invention provides the alloy for hydrogen selective synthesizing golden film, and it includes first aspect present invention Vanadium alloy.In some embodiments, hydrogen selective synthesizing golden film includes at least one tubular film.

The third aspect of the present invention provides the purposes of the alloy for hydrogen selective synthesizing golden film, and the alloy includes the present invention The vanadium alloy of first aspect.In some embodiments, hydrogen selective synthesizing golden film includes at least one tubular film.

The method that the fourth aspect of the present invention provides manufacture vanadium alloy, it includes：

Form the vanadium alloy of first aspect present invention；And

Formed vanadium is heat-treated at 800 DEG C~1500 DEG C of temperature and the pressure of 50MPa~500MPa to close Gold,

It is applied to the refining vanadium alloy of the deformation processing for forming light-wall pipe so as to be obtained.

Presence of the mechanical breakdown of alloy generally with hole is relevant and relevant with low elongation during pipe manufacture, and this is low Elongation is attributed to poor micro-structural, the uneven distribution of such as crystallite dimension or nonequiaxial crystal grain.Therefore, from into From the perspective of shape, it is generally desirable to the micro-structural of alloy is formed with little crystallite size and narrow size distribution.Further preferably with Minimum (or minimize) porosity formation alloy.Casting (casting) and other forming technologies produce composition uniformly but The uneven alloy of micro-structural.In the second aspect of the present invention, crystallite dimension becomes more meticulous and bigger micro-structural Uniformity is accomplished by the following way：

I) to the grain refining element that first aspect present invention definition is added in alloy；And

Ii) heat treatment step.

It is not intended to be limited by any one theory, applicants have found that in environmental pressure (0.1MPa) and moderate temperature model Enclose the normative heat treatment under (200 DEG C~600 DEG C) several for reducing porosity and optimizing micro-structural by recrystallization Without effect, reason is the liquidus curve high and solidus of V-Al alloys (for example, V₉₅Al₅The fusing point of alloy exceedes 1900℃).Therefore different heat-treatment protocols are needed.

The micro-structural that heat treatment step of the invention strengthens formed vanadium alloy by applying temperature and pressure is uniform Property.Compared to the same alloy casting without the heat treatment step, the vanadium alloy of refining has smaller crystalline substance evenly Grain distribution and the preferred porosity for reducing.This micro-structural enhances the formability of alloy, including the exhibition for improving alloy Ductility.The ductility of the vanadium alloy of refining is preferably greater than 10% elongation, and preferably greater than 11% extends, more preferably greater than Or equal to 12% elongation.In some implementation methods, the ductility of the vanadium alloy of refining is more than or equal to 13% elongation, Preferably greater than or equal to 14% elongation, more preferably equal to or greater than 15% elongation, more preferably 11% elongation~ 20% elongation, more preferably 13% elongation~20% elongation, the elongation of still more preferably 13% elongation~18% Rate, still more preferably 11% elongation~19% elongation.

The method of the present invention preferably produces vanadium of the crystal grain Linear intercept (grain linear intercept) less than 5.0mm to close Gold, crystal grain Linear intercept is preferably smaller than 5.5mm, preferably smaller than preferably smaller than 4.0mm, 4.5mm, even more excellent Choosing be less than 3.0mm, also preferably less than 2.0mm, and more preferably less than 1.0mm, its be all based on 6 crystal grain, It is preferred that 8 smallest sample amounts of crystal grain.

In certain embodiments, micro-structural includes skeleton (dendrite).In these embodiments, it is based on The smallest sample amount of 6 crystal grain, preferably 8 crystal grain, crystal grain Linear intercept value is preferably smaller than 500 microns, preferably small It is more preferably 50 microns~450 microns, more preferably 50 microns~400 microns, even more excellent in 450 microns Elect 50 microns~300 microns, more preferably 100 microns~350 microns, still more preferably 100 microns~200 as Micron.

Further, it is also preferred that, the vanadium alloy of refining is more than any hole (void) of 0.5mm not comprising average-size, The average-size in hole is preferably no greater than 0.4mm, is preferably no greater than 0.3mm.Can be using " the Stream of Olympus Essential " image analysis softwares determine crystal grain Linear intercept using ASTM E112-113 methods.Unless otherwise mentioned, Crystal grain Linear intercept is the survey of vertical with grain growth direction width in the anisometric situation of crystal grain (such as column) Value.

Manufacturing process may include to produce any suitable manufacturing process of composition homogeneity in the alloy for being formed.One In a little implementation methods, manufacturing process includes casting method, such as at least one in arc melting method or induction melting. In a preferred embodiment, manufacturing process includes at least in successively arc melting method or Cold crucible induction melting method Kind.Manufacturing process may include to form alloy pig or billet (billet).

Heat treatment step may include that alloy that can be to being formed applies any suitable process of required temperature and pressure. In one embodiment, heat treatment step includes high temperature insostatic pressing (HIP) (HIP) process.HIP be related to one section regulation when It is interior while applying moderate pressure high.

The applying of temperature and pressure is all important for the crystal grain needed for acquisition and micro-structural refining.Heat treatment step The rapid temperature for including making 1000 DEG C~1400 DEG C of the vanadium alloy experience, preferably 1050 DEG C~1380 DEG C, more preferably It is 1100 DEG C~1300 DEG C, more preferably up to 1350 DEG C of temperature, even more preferably from most 1400 DEG C of temperature. In one embodiment, heat treatment step is carried out at a temperature of about 1200 DEG C, preferably 1150 DEG C~1250 DEG C. Similarly, heat treatment step includes making vanadium alloy experience 50MPa~400MPa, preferably 75MPa~350 The pressure of MPa, more preferably 100MPa~300MPa.In one embodiment, heat treatment step is about 200 Carried out under the pressure of MPa, preferably 150MPa~250MPa.

Heat treatment step is generally carried out with the time span selected.In some embodiments, heat treatment step persistently enters Row at least 30 minutes, preferably at least 45 minutes, more preferably at least 1 hour, preferably at least 1.5 hours, more preferably At least 2 hours.It should be understood, however, that the duration depends on composition, consumption and the configuration of the alloy through being subject to processing.

The firing rate and cooling velocity applied on alloy during heat treatment step can also influence to refine result.At some In implementation method, at least one of firing rate or cooling velocity are at least 4K/ minutes, preferably at least 4.5K/ Minute, preferably at least 5K/ minutes, more preferably 4K/ minutes~10K/ minutes, preferably 5K/ minutes~9K/ Minute, and still more preferably 4K/ minutes~8K/ minutes.

Heat treatment step is preferably carried out in the inert atmospheres such as argon.

In the exemplary embodiment, casting alloy undergoes following condition：

1200 DEG C of temperature；

The pressure of 200MPa；

Continue 2 hours；

The heating/cooling rate of 5k/ minutes；With

Argon atmosphere.

The fifth aspect of the present invention provides the alloy of the tubular film for catalytic film reactor, and it is included with the present invention the The vanadium alloy that the method for four aspects is formed.

The method that the sixth aspect of the present invention provides manufacture tubular film, it includes：

Method according to a fourth aspect of the present invention forms the vanadium alloy of refining；And

The vanadium alloy of refining is formed as into light-wall pipe.

Tubular film can have as described above any suitably sized.As described in more detail below, in some embodiment party In formula, light-wall pipe includes that external diameter is that 2mm~25mm, preferably 3mm~20mm and wall thickness are 0.05mm~1 The pipe of mm, preferably 0.1mm~1.5mm.

It should be understood that the manufacture of pipe is multistep process, first relating to manufacture has required composition, micro-structural and chi Then these rods are deformed into required net shape by very little rod.Any suitable deformation method can be used to form pipe, Including drawing, rolling, extrusion casting, rod casting or its combination.

The seventh aspect of the present invention provide with the method for sixth aspect present invention formed for catalytic film reactor Film.The film can have various configurations, such as platypelloid type or tubulose.In a preferred embodiment, the film includes pipe Shape film.

The eighth aspect of the present invention provides catalytic film reactor (CMR), and it includes at least one with the 6th side of the invention The tubular film that the method in face is formed.

Film of the invention can have any suitable configuration.In some embodiments, the film may include substantially flat Film.In other embodiments, the film includes at least one pipe.It should be understood that the choosing of the various configurations of film It is specific advantages that specific CMR configurations bring to select based on the configuration.

CMR is substantially two-dimentional device, and it conveys synthesis by the catalyst bed adjacent with film along a dimension Gas.Planar film is more easily manufactured and more cheap than tubular film, but because the film is sealed around its outer rim, it has Bigger sealing area.This kind of sealed configuration provides bigger sealing area, and therefore may be easy to occur in raffinate And the leakage between penetrant air-flow.Tubular film makes it possible for tubulose CMR, therefore can reduce sealing area. In a tubular reactor, it is only necessary to sealed (usually compression seal) in each end of pipe.

In some embodiments, film of the invention has tubular configuration, preferably includes pipe.The pipe can have any Required size.In some embodiments, external diameter be 2mm~25mm, preferably 3mm~24mm, preferably It is 5mm~15mm, preferably 6mm~13mm, more preferably 8mm~12mm.In some implementation methods In, thickness of pipe wall is less than or equal to 1mm, preferably preferably 0.1mm~1.5mm, 0.05mm~1mm, more Preferably smaller than 0.5mm, more preferably less than or equal to 0.2mm.In an illustrative embodiments, tubular film tool There is following specification：

Length >=1000mm

External diameter：9.52mm(3/8”)

Wall thickness≤0.2mm

Alloy film is metal hydride, wherein the atomic hydrogen for dissolving occupies the interstitial site between metallic atom.Vanadium is hydrogenated Thing can take one of two kinds of principal modes under the temperature and pressure related to metal film, both principal modes be α- (it is identical with base metal in crystallography, and wherein hydrogen atom is randomly dispersed in body-centered cubic main body for hydride Gap in) and β-hydride (it is different from α-hydride in crystallography, and wherein hydrogen atom is in body-centered four in an orderly manner In gap in square main body).α phases and β phases can coexist under some concentration/temperature conditionss.However, most of In the case of, the marked difference of the lattice dimensions between these phases causes significant stress in alloy, and it can show The corrugation (best-case) or fragmentation (worst case) of alloy.Therefore, in shutdown of CMR comprising alloy film etc. During, this kind of phase in version is preferably avoided in cooling film.

As it was previously stated, the composition of selection alloy of the present invention to avoid this kind of phase in version in operation.In this respect, Hydride phase transition temperature in V-Al alloys is (wherein, for V₉₀Al₁₀(at.%), T_C<30 DEG C) be it is favourable, can This kind of phase in version is avoided to use it to.By contrast, the transition temperature of V-Ni is (for V₉₀Ni₁₀For>400℃) With the transition temperature of V-Cr alloys (for V₉₀Cr₁₀For>200 DEG C) these alloys can not be made in required opereating specification Phase in version is avoided in (such as 0 DEG C~500 DEG C).In fact, when room temperature is cooled to from about 400 DEG C of operation temperature, The use of these alloys increased brittle break.

Can advantageously make CMR in the operation temperature from about 400 DEG C using the alloy film formed by vanadium alloy of the invention Shut down at a temperature of degree to usually less than the 30 DEG C room temperatures of (preferably 20 DEG C~30 DEG C), wherein reactor is in operability Hydrogen and operation in the Typical ranges (typically larger than 0.05) of the ratio between metal (H/M), and film does not suffer from α to β phase in version. The operation of CMR can include：Startup and shutdown work within the temperature range of including its operation temperature and environment temperature Sequence, and phase in version is not suffered from, so as to allow simply to operate reactor.This permission CMR and film can be by more Individual operation circulation is used, and in operation circulation CMR is activated, operates and shuts down.In particular, it is to avoid stop The brittle break of the film caused due to phase in version during machine.

Therefore, the method that the ninth aspect of the present invention provides operation catalytic film reactor, it includes：

The catalyst film reactor comprising at least one tubular film is provided, the tubular film includes first aspect present invention Vanadium alloy or formed with the method for sixth aspect present invention；And

When reactor is in 0 DEG C~350 DEG C of operation temperature, with the ratio between the hydrogen more than 0.05 and metal (H/M) behaviour Make catalytic film reactor.

The step of operation catalytic film reactor, may include multiple operations, including the reactivity operation of reactor, reactor Start and shut down operation and other any reactor applications or operation behavior and/or the process of those conditions can be used.

In some embodiments, operation temperature be 20 DEG C~300 DEG C, preferably 25 DEG C~275 DEG C, more preferably 30 DEG C~250 DEG C, even more preferably 40 DEG C~200 DEG C.Similarly, in some embodiments, H/M is than big In 0.1, preferably greater than 0.15, preferably greater than 0.2, preferably greater than 0.25, even more preferably greater than 0.3.

Compared to the catalytic film reactor comprising the tubular film formed by vanadium or other conventional vanadium alloys, with containing the present invention Vanadium alloy/refining vanadium alloy tubular film catalytic film reactor provide significant operational advantage.For V and its Its V alloy, α to β phase in version occurs under operating condition as described above.Any phase in version can be naturally Ground influence property, so as to influence the life-span of tubular film.Therefore, with containing vanadium alloy of the invention/refining vanadium alloy The catalytic film reactor of tubular film can advantageously start, at the reaction temperatures operation and within the scope of temperature wider and H/M than condition (>0.05) shut down under, and the condition in reactor, particularly H/M ratios need not be significantly changed.

The operation of reactor includes the startup of reactor and shuts down operation.Startup generally includes to heat reactor from room temperature To operation temperature.Shutdown generally includes for reactor to be cooled to another temperature from operation temperature, usually room temperature.In addition, Room temperature preferably includes environment temperature.In some embodiments, room temperature include less than 30 DEG C, preferably 10 DEG C~30 DEG C, More preferably 20 DEG C~30 DEG C.

In some embodiments, operating condition includes the cooling step of catalytic film reactor, it preferably includes catalytic membrane The environment cooling of reactor.It should be appreciated, however, that other cooling schemes can be used, such as it is cold using heat exchanger etc. But the supplement heat rejecter of device, fluid cooling or convection current cooling etc..

It should be appreciated that unless otherwise mentioned, the average of at least six measured values is defined as into experiment parameter.

The tenth aspect of the present invention provides the film of the catalytic film reactor to contain light-wall pipe, and the light-wall pipe is included Vanadium alloy, the vanadium alloy includes：Vanadium；Content is the aluminium more than 0at%~10at%；0.01at% is less than with content Ta；The ductility of the vanadium alloy is more than 10% elongation, preferably greater than 11% elongation.

It should be appreciated that the alloy content and engineering properties (particularly ductility) of the film of tenth aspect present invention with above for It is identical that first and second aspect of the present invention is described, and should be appreciated that it is equally applicable to this tenth aspect of the invention.

In some embodiments, also comprising the grain refining element selected from Ti, Cr, Fe, Ni or B, it contains film Amount is more than 0~5at%, preferably 0.2at%~4.5at%.In some embodiments, grain refining element Content is 0.1at%~2at%, more preferably preferably 0.1at%~2at%, 0.1at%~1at%.

In some embodiments, the crystal grain Linear intercept of vanadium alloy is less than 5.0mm, preferably smaller than 5.5mm, excellent Choosing is less than 4.0mm, also preferably less than preferably smaller than 4.5mm, even more preferably less than 3.0mm, 2.0mm, And more preferably less than 1.0mm, its smallest sample amount for being all based on 6 crystal grain, preferably 8 crystal grain.

In certain embodiments, micro-structural includes skeleton.In these embodiments, based on 6 crystal grain, It is preferred that 8 smallest sample amounts of crystal grain, crystal grain Linear intercept value is preferably smaller than 500 microns, preferably smaller than 450 microns, More preferably 50 microns~450 microns, more preferably 50 microns~400 microns, even more preferably 50 microns~ 300 microns, more preferably 100 microns~350 microns, still more preferably 100 microns~200 microns.

Further, it is also preferred that, the vanadium alloy of refining is more than any hole of 0.5mm not comprising average-size, empty The average-size in cave is preferably no greater than 0.4mm, preferably no greater than 0.3mm.Can be using " the Stream of Olympus Essential " image analysis softwares determine crystal grain Linear intercept using ASTM E112-113 methods.Unless otherwise mentioned, Crystal grain Linear intercept is the survey of vertical with grain growth direction width in the anisometric situation of crystal grain (such as column) Value.

In embodiments, vanadium alloy is to have been subjected to the temperature and 50MPa~500MPa at 800 DEG C~1500 DEG C Pressure under heat treatment refining vanadium alloy.In embodiments, heat treatment include make vanadium alloy experience 1000 DEG C~ 1400 DEG C of temperature, preferably 1050 DEG C~1380 DEG C, more preferably up to 1400 DEG C of temperature, still more preferably About 1200 DEG C.In embodiments, heat treatment step includes the pressure for making vanadium alloy experience 50MPa~400MPa, Preferably 75MPa~350MPa, even more preferably about 200MPa.

In embodiments, the ductility of the vanadium alloy of refining is more than 10% elongation, preferably greater than or equal to 11% Elongation, more preferably equal to or greater than 13% elongation, also more preferably more than or equal to 14% elongation.

The eleventh aspect of the present invention provides the catalytic film reactor with thin-walled periosteum, and the thin-walled periosteum includes vanadium Alloy, the vanadium alloy includes：Vanadium；Content is the Ta of aluminium and content more than 0at%~10at% less than 0.01at%； The ductility of the vanadium alloy is more than 10% elongation, preferably greater than 11% elongation.

It should be appreciated that the eleventh aspect of the present invention can include the whole features above for tenth aspect present invention description.

Brief description of the drawings

Now with reference to the Description of Drawings present invention, accompanying drawing illustrates particularly preferred embodiment of the present invention, wherein：

Fig. 1 provides the H to (a) V-Al and (b) V-Cr (lower section) measurements at 400 DEG C₂Flux (J, for film thickness Inverse normalized, x) with feeding H₂The figure of pressure.

Fig. 2 is provided and vanadium and (a) V-Al and (b) V-Cr alloys is measured under different hydrogen dividing potential drops (p) at 400 DEG C Hydrogen absorb (r is expressed as H/M ratios) figure.

Fig. 3 is provided at 400 DEG C through (a) V-Al and concentration dependent diffusion coefficient (D of the hydrogen of (b) V-Cr alloys_H) Figure.

Fig. 4 shows the V under (a) 673K and (b) 623K_90-XTi_XAl₁₀The hydrogen permeability for calculating in alloy is not with With the change of feed pressure.

Fig. 5 provides the V under (a) 673K and (b) 623K_90-XTi_XAl₁₀Dissolved under different hydrogen pressures in alloy The figure of hydrogen concentration (r, in units of atomic hydrogen/metal ratio) change.

Fig. 6 shows the V under (a) 673K and (b) 623K_90-XTi_XAl₁₀Average hydrogen diffusion coefficient (D in alloy_H) with hydrogen The change of concentration (r).

Fig. 7 provides five electron micrographs (BSE patterns) of following alloy：(a)V₈₈Ti₂Al₁₀；(b)V₈₆Ti₄Al₁₀； (c)V₈₄Ti₆Al₁₀；(d)V₈₂Ti₈Al₁₀；(e) V₈₀Ti₁₀Al₁₀。

The H that Fig. 8 provides V-Ni, V-Al and V-Cr alloy under 400 DEG C and 10 bars absorbs the figure for reducing.

Fig. 9 shows the hydrogen diffusion coefficient (D of V-Ni, V-Al and V-Cr alloy at 400 DEG C_H) and hydrogen concentration between Relation.

Figure 10 shows the influence of Ni, Cr and Al to pressure dependency absorption (H/M) under 400 DEG C of operation temperature.

Figure 11 illustrates the X-ray diffraction measurement value during 0.20MPa of situations below：(a)When V；(b)When V₉₀Cr₁₀；(c)When V₉₀Ni₁₀；(d) When V₉₀Al₁₀。

The X-ray diffraction that Figure 12 illustrates the following alloy for being cooled to environment temperature from 400 DEG C under the hydrogen of 1 bar is surveyed Value：(a)V₉₀Ni₁₀(atom %, left side)；(b)V₉₅Al₅Alloy；(c)V；(d) V₉₀Al₁₀。

Figure 13 provides the chart of SEM image of enclosing, which show V₈₅Ni₁₅Alloy before heat treatment after elongation, Wherein (a) is to provide each sample the % charts of elongation；B () is the SEM image of cast alloy；C () is through 1000 DEG C The SEM image of the alloy of heat treatment；D () is through 1200 DEG C of SEM images of the alloy of heat treatment.

Figure 14 shows the V without grain refiner₉₅Al₅The optical microphotograph section of ingot.

Figure 15 shows the V with grain refiner₉₅Al₅The optical microphotograph section of ingot.

Figure 16 provides as cast condition V₉₅Al₅The optical microscope image of alloy.

Figure 17 is provided has B in the cylindrical region vertical with grain growth direction_0.1Ti_0.5(wt%) grain refiner As cast condition V₉₅Al₅The optical microscope image of alloy.

Figure 18 is provided has B in equiaxial region_0.1Ti_0.5(wt%) the as cast condition V of grain refiner₉₅Al₅The light of alloy Learn MIcrosope image.

Figure 19 is the photo of the alloy pig prepared by " successively " technique, wherein (a) is the side view of the ingot；B () is this The top view of ingot.

Figure 20 provides the light micrograph of V-Al alloys before HIP is processed.

Figure 21 provides the light micrograph of V-Al alloys after HIP treatment.

Figure 22 illustrates the schematic diagram of catalytic film reactor.

Figure 23 provides the photo of prototype tubulose CMR.

Figure 24 provides the photo at the interface between vanadium alloy pipe and plating Pd catalyst layers.

Figure 25 provides V and V₉₀Al₁₀Avoid α to β phase in version needed for operation temperature and H/M than contrast.

Specific embodiment

The present invention relates to a kind of alloy, the method and the alloy and refined alloy of the refined form for manufacturing the alloy As the purposes of the tubular film for being suitable for catalytic film reactor (CMR).

Alloy is selected

Selected alloy is vanadium class alloy, and it has following solid solution formula：

V_100-(Y+Z)Al_YX_Z

Wherein X=Ti, Cr, Fe, Ni, B；Y is>0~10；And Z is 0~5.

Inventors determined that vanadium class alloy should to show following key characteristic optimal to be obtained in CMR reactors Use：

- good diffusivity/absorptance, to enable to realize height while hydrogen embrittlement effect is minimized H₂Permeability；

- good formability, including good ductility (at least 10% elongation) so that can be preferably used existing Deposit or known manufacturing process manufactures the alloy film of desired configuration；With

- mechanical stability, in particular, α to β hydrogenation phase transitions is suppressed to shut down temperature in desired CMR Degree is near or below, it means that these alloys can be in the common operation temperature (such as 400 DEG C) of CMR and (lower ) between shutdown temperature (such as environment temperature) circulation and do not suffer from the phase transformation of potential calamity.

Applicant carried out substantial amounts of tentative trial determining the V alloy (being described in detail below) being best suitable for.Research Many alloys, including V-Al, V-Ni and V-Cr class alloy.

Selection experiment 1：V-Al, V-Cr and V-Ni

Method and material

Select several binary V-Al (V₉₅Al₅、V₉₀Al₁₀、V₈₅Al₁₅、V₈₀Al₂₀、V₇₅Al₂₅, it is with atom % Expression) and V-Cr (V₉₅Cr₅,V₉₀Cr₁₀,V₈₅Cr₁₅) alloy to form single-phase body center cubic solid solution to ensure.

With wire cut EDM come the ingot of arc cutting melting, circular membrane is thus prepared.Chemistry checking alloy composition, It is in 2% (relative) for demarcating composition.In Dolan MD.Non-Pd BCC alloy membranes for industrial hydrogen separation.J Membr Sci 2010；362(1-2):12-28 (hereinafter referred to " Dolan 2010 " 500nm thickness Pd is described in, it is thus understood that be incorporated by this specification its content by this) in detail to urge The preparation method of agent layer, including surface treatment and deposition.Film is about 900mm thickness so that it is guaranteed that body diffusion is that hydrogen oozes Rate-limiting step in thoroughly.

Hydrogen flux is measured with constant-voltage method.With inconel module, (it is heated to 400 DEG C and keeps under an inert atmosphere 12 hours) in copper washer by film compression seal.To be enough to prevent the speed of concentration polarization to feed surface supply 10% CO₂In H₂In mixture.Additionally, to be enough to prevent the speed of concentration polarization from feeding Ar to opposite surface.Often The condition of kind maintains ensure to reach stable state circulation condition for about 1 hour.Feed pressure is gradually increased to about from about 1 bar 10 bars (a), while purging pressure is maintained into about 1.5 bars (a) in whole experiment.Using for Valuation Standard gas Mixture calibration gas-chromatography come measure infiltration logistics in H₂Content.It is then based on penetrant H₂Concentration and Ar Flow velocity calculate flux.The CO detected in logistics is permeated₂Represent the defect of film, and correspondingly termination test.

Absorbed with the hydrogen that pressure measurement mode measures every kind of alloy.Sample is kept for 24 hours with true in 400 DEG C under vacuo Guarantor removes any remaining H from flux measurement from sample₂.Then isothermal is produced between about 15 bar~0 bars Line, first with 15 bar absorption steps, then carries out progressively desorption procedure.

Lattice parameter measurement is carried out after infiltration and absorption test.Alloy is ground with Philips planetary micro mills Clay into power.These powder are sealed into glass tube under vacuo, then carried out at 450 DEG C 16 hours go should Power is calcined.The Bruker of (40kV, 40mA) is radiated using the utilization CuK α for being equipped with LynxEye silicon strip detectors D8Advance X-ray diffractometers obtain XRD case.With the step-length of 0.02 ° of 2 θ and often walk the counting of 3.2 seconds Time, powder sample is scanned in 20 °~130 ° of 2 θ scopes.With Diffrac.Topas software kits (Bruker AXS) really Determine lattice parameter.

As a result

X-ray diffraction measurement confirms that each alloy is single-phase vanadium solid solution (VSS).

Fig. 1 shows the flux of the alloy measurement to V-Al and V-Cr series at 400 DEG C with the hydrogen dividing potential drop (p of feeding₁) Change.In each situation, by flux for film thickness normalization reciprocal, to correct each membrane sample between sample it is thick The fine difference of degree.Hydrogen dividing potential drop (the p of impermeable surface₂) be not calculated in yet in because it is compared with feed pressure It is small to ignoring.Some trend are obvious.Firstly, for each alloy series, flux is with Al or Cr contents Increase and reduce.Secondly, the amount of flux of V-Cr alloys is more than corresponding V-Al alloys.

According to Fick's 1st law of diffusion, the flux by the solute (H) of solvent (V classes alloy) is the diffusion coefficient of solute With the product of concentration gradient.Know that the dissolving hydrogen concentration at hydrogen dividing potential drop corresponding with amount of flux shown in Fig. 1 just can be calculated Go out by the H diffusion coefficients of each alloy.

Fig. 2 shows a series of hydrogen absorption isotherms corresponding to each alloy series at 400 DEG C, and it is expressed as being directed to The dissolving hydrogen concentration r (unit is atomic hydrogen/metal ratio, or H/M) of hydrogen dividing potential drop (p).In addition, being also shown for not in each figure The absorption isotherm of the vanadium of alloying is for reference.The absorption data of V do not show plateau, and (plateau, can represent α/β is changed), but shown obvious turn really (this expression has approached the condition that α/β conversion can occur).Al's Addition causes that this turn becomes more indefinite, shows that Al stabilizes V to resist the formation of β-hydride.V-Cr Thermoisopleth has the shape similar to the thermoisopleth of V, presents obvious flex point.Different from Al, Cr seems not making V stabilizes to resist the formation of β-hydride.When alloy is possibly subjected to can this condition for hydrogenating phase transition When, when stability of these films during thermal cycle is assessed, this is important Consideration.This can be more detailed below Carefully illustrate.

According to preceding method (Dolan MD, McLennan KG, Way JD.Diffusion of atomic hydrogen through V-Ni alloy membranes under nondilute conditions.J Phys Chem C 2012； 116(1):1512-8 is (hereinafter referred to " Dolan 2012 ", it is thus understood that its content is incorporated by into this specification by this In), using in charging (r₁) and penetrant (r₂) flux that measures at surface and corresponding H/M values calculated at 400 DEG C Concentration dependent diffusion coefficient (the D of each alloy_H)。

For each bianry alloy series, V is substituted by Al or Cr and reduces Hydrogen diffusion coefficient D_H, and such as Fig. 3 Shown, Al is acted on more than Cr diffusible reduction.Each alloy also presents stronger concentration dependent, wherein D_H Increase with the increase of dissolving hydrogen concentration.

Dolan 2012 based on above-cited V-Ni systems is studied, there is provided herein two kinds of binary vanadium class alloy bodies It is the contrast of (V-Al and V-Cr).In the compositing range studied, each alloy in these series all forms single-phase Body-centred cubic solid solution.This trend is not reflected in hydrogen absorbent properties, and two kinds of alloy elements all reduce hydrogen suction Receive, and the most pronounced effects of aluminium.

The hydrogen diffusivity of calculating follows V-Cr>V-Al>The trend of V-Ni, and the diffusivity of all alloys all shows Stronger concentration dependent.

Selection experiment 2：V-Ti-Al alloys

Method and material

Devise Formula V_90-XTi_XAl₁₀Alloy series, wherein X=0,2,4,6,8 and 10, so that it is guaranteed that 100% V_SSMutually formed, and the clear explanation that instead of V hydrogen how will be influenceed to convey by Ti is provided.This will determine the property of Ti Whether matter can be used to be developed for high temperature H₂/CO₂Separate the sane hydrogen separation membrane with membrane reactor application.

Film is prepared as described in Dolan 2012, the surface of each membranous disc is polished and is coated with Pd layers of 500nm To make hydrogen migration resistance in interface minimum.The thickness of each film is about 900mm to ensure that the bulk transport of hydrogen is infiltration Rate-limiting step.Sample from identical ingot is installed and polished, then with backscattered electron (BSE) pattern in scanning electricity Checked in sub- microscope.

Hydrogen flux is measured in 623K and 673K with constant-voltage method, wherein feed pressure and penetrant pressure are maintained at Steady state value is until recorded constant H₂Untill flux (usual 1800 seconds~3600 seconds).Will with the increment of 0.1MPa Feed pressure is incrementally increased to the maximum of 1.0MPa, and penetrant pressure is maintained into 0.15 for all measurements MPa.Purge gas (Ar) are used on penetrant side, and changes flow velocity to ensure the H in Ar₂Content is 1% To 5%.With the H in gas Chromatographic Determination purge gas₂Content, to H in required concentration range₂Calibrated.

In 623K and 673K, the overall hydrogen of each alloy in 0~1.5MPa is measured using Sieverts methods Absorb.First carry out 1.5MPa absorption steps and then progressively carry out desorption procedure until 0MPa, thus measures absorption Thermoisopleth.Measured with same sample and absorb and permeate to ensure uniformity.

Lattice parameter measurement is carried out after infiltration and absorption test.Alloy is ground in planetary mill and Calcined under the nitrogen of 723K 60,000 second, to mitigate stress and remove the hydrogen of residual.Walk with 0.02 ° of step-length and often The gate time of 3.2 seconds, uses Cu-K α source record XRD cases in 20 °~130 ° of 2 θ scopes.Use Diffrac.Topas Software kit (Bruker) refines lattice parameter.

As a result

Fig. 4 shows the V for being in 673K (upper figure) and 623K (figure below)_90-XTi_XAl₁₀Alloy in series, It is assumed that p^-0.5The hydrogen permeability calculated during concentration dependent with different feed pressures change.In each situation, calculate Permeability substantially reduced with the increase of feed pressure, show to have deviated from preferable Sieverts types behavior.Although Multiple trial is carried out, but the permeability of several alloys cannot have all been measured in 623K, reason has been that the fragility of alloy is broken It is bad.For those alloys all measured at a temperature of two kinds, permeability increases with the reduction of temperature.One series Interior curve is almost overlapped, and is shown in the compositing range studied, and substitute V by Ti influences very on infiltrative Small (such as p^-0.5Determined in the figure of pressure dependency).

Fig. 5 is shown for V_90-XTi_XAl₁₀A series of hydrogen at the several temperature of all alloys in series absorb Thermoisopleth.In the presence of obvious compositing dependence, wherein the hydrogen concentration (r) for dissolving increases with the increase of Ti contents.673K Thermoisopleth is almost straight line, but turn in 623K in entire series is indicated close to but do not enter into (α-hydride + β-hydride) two phase region situation.

According to Fick's 1st law of diffusion, by the hydrogen flux (J) that will measure divided by hydrogen concentration gradient (d_C/d_x) calculate Average hydrogen diffusion coefficient in V-Ti-Al alloys.By the corresponding feed surface (r of dissolved hydrogen₁) and penetrant surface (r₂) Concentration, calculate and each flux measurement corresponding concentration gradient of value.

Fig. 6 shows the hydrogen diffusivity of each alloy during 673K and 623K with the change of average hydrogen concentration.In each situation Under, there is strong hydrogen concentration dependence, and D_HIncrease with the increase of r.Also there is obvious compositing dependence, its In for give r, D_HReduced with the increase of Ti contents.These data with observe Ti dependences absorb and Ti dependent/non-dependents permeability is consistent, because absorb effectively being cancelled out each other with diffusivity trend.

Crystal grain refinement

There is increase hydrogen to absorb while reducing the diffusible effect of hydrogen to substitute V by Ti.Under the background of alloy film development, The two is all to main body V₉₀Al₁₀The unfavorable of the property of alloy is modified, and is absorbed (to make with previously mentioned reduction The related destruction of fragility is minimized) and diffusivity is maximized (to make infiltration rate maximize without causing machinery Loss) purpose it is opposite.

As shown in fig. 7, (a) V₈₈Ti₂Al₁₀、(b)V₈₆Ti₄Al₁₀、(c)V₈₄Ti₆Al₁₀、(d)V₈₂Ti₈Al₁₀(e) V₈₀Ti₁₀Al₁₀Respective electron micrograph relatively shows each alloy only comprising single-phase, the wherein difference reflection of shade Different crystal grain orientations.Additionally, crystallite dimension is reduced with the rising of Ti contents, its from 2%Ti when>500 μm it is down to about 100 μm during 10%Ti.V₉₀Al₁₀The micro-structural of alloy is shown with past research About 1000 μm of crystallite dimension.It is thin for the crystal grain of V, more particularly V-Al alloys that these results show that Ti serves as Agent, reduces V_SSThe crystallite dimension of phase.

The selection of alloy

In terms of hydrogen diffusivity, the above results indicate the diffusivity that Ni, Cr, Al and Ti significantly reduce hydrogen. However, being different from Ti, Cr, Ni and Al reduce absorption, which give bigger brittle resistance.This shows three Plant tool promising Binary Alloy System V-Ni, V-Al (also referred to as V-1) and V-Cr (also referred to as V-2) is applicable to close Golden CMR.Applicability to these alloy systems has carried out more detailed research.

A. hydrogen absorbs

Weaken the hydrogen in vanadium to absorb so as to improve the Main Means of intensity is alloying.

Applicant have discovered that Al, Ni and Cr give favourable hydrogen absorbent properties, but Ti does not have.In fact, hydrogen Absorption reduced with the increase of Al, Ni and Cr content, so as to improve the resistance to hydrogen embrittlement.

Al(V-1–V₉₅Al₅)、Ni(V₉₅Ni₅) and Cr (V-2-V₉₅Cr₅) at 400 DEG C and the p (H of 10 bars₂) when to vanadium Hydrogen absorb effect compare figure 8 illustrates.When being alloyed to 15at%, each element reduces absorption 50%~60%.

B. mass transport

Hydrogen can be subject to hydrogen concentration (its of film thickness, temperature, each Surface absorption by conveying through the transmission rates of alloy film With alloy composition and hydrogen dividing potential drop about) and hydrogen permeability influence.

Fig. 9 shows the relation between the hydrogen concentration and diffusivity of the three kinds of V class alloys studied at 400 DEG C. In alloy shown in each, hydrogen diffusivity increases with the increase of hydrogen concentration.The hydrogen that curve on figure represents constant leads to Amount, i.e. alloy and the alloy with less D and larger H/M with larger D and relatively low H/M With identical performance.Cause hydrogen embrittlement and mechanical breakdown because hydrogen high absorbs, and diffusivity does not cause mechanical loss, So preferably diffusivity/absorption curve intersects with the dotted line towards the figure upper left corner.Based on this standard, V-Al (V-1) Alloy is very excellent, is then respectively V-Cr (V-2) and V-Ni alloys.

Figure 10 show Ni, Cr and Al all reduce absorption (be expressed as hydrogen atom and the ratio between metallic atom of dissolving, Or H/M), and diffusivity is reduced as shown in Figure 9.Although it reducing overall hydrogen permeability, permeability is far high Mean that certain permeability reduction can be tolerated while acceptable hydrogen yield is still transmitted in the fact Pd.

C. phase stability

Metal hydride can use two kinds of principal modes --- and (there is α-hydride the body-centered for being incorporated to gap hydrogen atom to stand for it One of square structure) and β-hydride (it has the body-centered structure of the quartet for being incorporated to gap hydrogen).Lattice dimensions between these phases Marked difference significant stress is caused in alloy, corrugation (best-case) or fragmentation that it may show alloy (worst case).Accordingly, it would be desirable to avoid the phase in version in operation.When during such as reactor is shut down from behaviour When being cooled to another temperature (such as environment temperature) as temperature, alloy film is most easily influenceed by this phase in version.

It is as described below in order to study the influence of the phase stability of vanadium during alloying condition is shut down to simulation, use X X ray diffraction light beam line unit carries out X-ray diffraction measurement to Vanadium hydride.

Material and method

It is prepared by alloy

Fine and close uniform V and V is prepared by high-purity V, Cr, Ni and Al by electric arc melting on water-cooled copper stove Class alloy (V₉₀Cr₁₀、V₉₀Ni₁₀、V₉₀Al₁₀, expressed with at.%) and ingot.For diffractometry, will using electro-discharge machining The ingot is cut into the disk of 0.8mm.Before the test, by each sample polishing with remove remnants oxide, plating with The Pd of 500nm calcines a few hours to promote between Pd and vanadium alloy to promote hydrogen absorption rate at 400 DEG C It is closely sealed.Sample is ground into corase meal for diffractometry.For absorptiometry, 1 is cut out from identical main ingot The piece of mm × 3mm × 10mm.

Diffractometry

Diffractometry is carried out in two single synchronized process.During each process, sample is loaded into quartzy capillary It is sealed against into static pressure sample cell in pipe and using the compression fittings with the graphite collar.The sample cell is connected to can The gas manifold of vacuum degassing and supercharging is carried out with static hydrogen.Sample is heated with hot gas pressure fan, the pressure fan is in bullet Installed perpendicular to X-ray beam at tubule wall 3mm.X-ray beam wavelength is calibrated with NIST SRM 660a (LaB6) And instrument parameter, and calibrate temperature as thermal expansion standard with Pd.

Measured with isobaric series, wherein pressure is maintained, and temperature is down to 30 from up to 450 DEG C in some steps ℃.Each serial pressure gradually increases.If detecting phase in version in isobaric series, fresh sample is loaded, so Start series below afterwards.

Using powder diffraction light beam line, in Australian Synchrotron, (Melbourne, Australia is big during in June, 2012 Leah) carry out initial measurement process.Entered with collimated light beam geometry and Mythen microstrip 1D detectors Row V₉₀Ni₁₀And V₉₀Al₁₀The powder diffraction measurement of alloy.Wavelength used isDuring measuring, pass through 5 ° of arcs vibrate the OD samples capillary of 0.7mm.With extreme condition (I15) light beam line during in March, 2013 in Diamond Light Source (Harwell, UK) are subsequently measured process.Using collimated light beam geometry and Perkin Elmer flat board 1621EN detectors, the sample installed with 1.5mm OD capillaries carries out V and V₉₀Cr₁₀ The powder diffraction measurement of alloy.Wavelength used isDuring measuring, sample is vibrated by 30 ° of arcs. Diffraction pattern is refined using the Diffrac.Topas Rietveld type software kits produced by Bruker AXS, so that really Lattice parameter is determined.

Figure 11 shows a series of X-ray diffractions of the vanadium at a temperature of the pressure of 0.20MPa and 30 DEG C~450 DEG C Pattern.The figure shows that vanadium exists at 200 DEG C~450 DEG C as Emission in Cubic, and as four directions when less than 200 DEG C Mutually exist, this is shown by the division at (011), (002) and (211) peak.This stagnation temperature with the Vanadium hydride reported Degree (T_C) be well matched with.V during for 0.20MPa₉₀Cr₁₀(Figure 11 b), (020) and (211) indicated at 200 DEG C The presence at peak represents and transformation is there occurs between 200 DEG C and 300 DEG C.For V₉₀Ni₁₀(Figure 11 c), it is faint at 400 DEG C (020) and (211) peak for existing represents that this transformation occurs the temperature at slightly above 400 DEG C.V₉₀Al₁₀(Figure 11 d) is all Under the conditions of all maintain cubic structure.

Similar result is shown in Figure 12, Figure 12 to show and be cooled to 1 Ba Qing in 400 DEG C under 1 bar hydrogen During environment temperature under partial pressure, (a) V₉₀Ni₁₀(atom %), (b) V₉₅Al₅Alloy, (c) V and (d) V₉₀Al₁₀ XRD case.Obviously, V₉₅Al₅And V₉₀Al₁₀Alloy maintains α-hydride until being down to 30 DEG C, and V-Ni Alloy forms β-hydride phase from 300 DEG C, and for pure V, from α-hydride to the transformation of β-hydride Occur at 190 DEG C.Similar experiment shows that V-Cr (V-2) crystallizes out β-hydride from 200 DEG C.

Addition Ni and Cr can all improve transition temperature.Transition temperature is decreased to less than 30 DEG C by the Al for adding 10at%. This allows film to experience thermal cycle in a hydrogen atmosphere (for example, opening in the CMR containing the alloy film with the composition During dynamic and shutdown) and it is not subjected to the phase in version that can cause rupture.

As shown in FIG. 11 and 12, it is clear that V-Al (V-1) alloy is optimal alloy, because its 30 DEG C for being studied~ Phase in version is not experienced within the temperature range of 400 DEG C.

D. oxygen content

Oxygen content is less than 0.15wt%.The vanadium of business form contains the dissolved oxygen of the level of signifiance.Oxygen is by the hydrogen with dissolving Reaction can cause embrittlement.Al and Ti remove oxygen from vanadium.

E. formability

The formability of V class alloy materials, especially for elongation for, determine and can be used to produce flat or tubulose The manufacture method of film.For example, generally show 25% in production in enormous quantities for manufacturing the alloy of tubular products~ 35% maximum elongation rate (by extrusion and drawing), and according to deformation processing, then elongation be at least 10%~ 20%.One example is that deforming for every time has a large amount of deformation processings calcined between reduction and passage.

In order to determine formability, the material character for studying three kinds of alloy systems (V-Ni, V-Al and V-Cr) is checked. V metals are also tested for build the benchmark of these alloys.Characterization for Microstructure and tension test has been carried out to measure these Alloy is in as cast condition and the elongation of calcined state.

F-1 sample preparations and experiment

Mix and melt simple metal in the cold crucible furnace of electric arc furnaces or sensing heating, and make it in water-cooled copper siege Upper solidification.Gained ingot is a diameter of 50mm and length is 8mm~10mm (electric arc melting) or 50mm~100 The cylinder of mm (Cold Crucible Melting).The sample for tension test is then cut out from ingot by camber line patterning method. These samples are fired to 1 hour more under oxygen-free atmosphere in 1250 DEG C.V-Ni alloys are stretched in order to study deformation The influence of rate long, the V of 0.4mm has been manufactured by electric arc melting and rolling₈₅Ni₁₅Alloy (at%) piece.Cutting stretching Sample simultaneously carries out the calcining of 1 hour at 1250 DEG C.Born with the crosshead speed of 0.05cm/ minutes, the maximum of 2KN Carry and the specification of 8.5mm carries out tension test.Because most of alloy is excessively crisp so that yield strength can not be recorded, So only measuring elongation and UTS.Ductility measurement has been carried out according to ASTM E8/E8M.

Vanadium

As shown in table 1, the maximum elongation rate of vanadium is 15% (3 average value of sample).

Table 1：The elongation and UTS (3 individually measurements) of vanadium

Composition	Condition	UTS(MPa)	Elongation (%)
				Pure V metals	As cast condition, is cast by electric arc melting	181	14
Pure V metals	As cast condition, is cast by electric arc melting	209	15
				Pure V metals	As cast condition, is cast by electric arc melting	136	16

Vanadium nickel alloy

The nickel that 5~15 atom % are added in vanadium causes ductility to completely lose, and the maximum elongation rate for being recorded is less than 1%.The elongation of the sample obtained by electric arc melting is slightly above the situation that cold crucible casts, and this is attributable to electric arc Alloy of the porosity of the alloy of melting less than cold crucible founding.

Table 2：The elongation and UTS of V-Ni alloys

Figure 13 shows V of the heat treatment to measured cold crucible casting₉₀Ni₁₀Elongation influence.1000 The calcining that 1 hour is lasted at DEG C reduces elongation, and this is the precipitation due to being unfavorable for the secondary phase of elongation.With Calcining heat is further increased to 1250 DEG C, and elongation recovers, but is still below 1%.V₈₅Ni₁₅The rolling sample of alloy Realize highest elongation, almost 2%.However, this can still be described as highly brittle alloy.

The V-Ni class alloys studied have low-down ductility, and this cannot be by alloying, casting, heat treatment Significantly improved with deformation.Suitable sheet material is formed as by existing industrial process this strongly limits this alloy Or the ability of tubing.

V-Al (V-1) alloy

As shown in table 3, V₉₅Al₅And V (5%)₉₀Al₁₀(10%) alloy shows stretching much larger than equal V-Ni alloys Rate long.

Table 3：The elongation and UTS of V-1 alloys

The V-Al classes alloy studied has sufficient ductility when with 5%Al, but in 10%Al less than reason The ductility thought.The result shows that the Al content less than 10% is desirable, preferably from about 5% content.This Alloy is most suitable for forming sheet material or tubing by existing industrial process.

V-Cr (V-2) alloy

The engineering properties of V-Cr alloys shows in table 4：

Table 4：The elongation and UTS of V-Cr alloys

The V-Cr class alloys studied have low-down ductility, and this cannot be by alloying, casting, heat treatment Significantly improved with deformation.Suitable sheet material is formed as by existing industrial process this strongly limits this alloy Or the ability of tubing.

F. alloy optimal properties

In the alloy studied, V-Al alloys clearly provide required hydrogen permeability, phase in version and engineering properties, It is significantly better than other Binary Alloy Systems (V-Ni and V-Cr) studied.Specifically, V-Al classes alloy has pipe Material manufactures engineering properties needed for (such as by tube-drawing, rolling or extrusion), and V-Ni and V-Cr alloys for It is excessively crisp for this manufacture method.With reference to favourable permeability, V-Al alloys are have selected, because it has more than satisfaction The unexpected excellent and optimal property of standard, particularly for other V alloys studied.

Of particular concern is V₉₅Al₅Alloy system, it has optimal compared to other binary systems studied Property.Note, the grain refining element (such as Ti, Fe, Ni or Cr) of addition 0~5% improve it is as described above into Shape and micro-structural.

G.V₉₅Al₅Crystal grain refinement

V is analyzed in the case of in addition and without grain refiner₉₅Al₅The micro-structural of alloy.

It is prepared by ingot

For the method for laboratory scale, in addition and without grain refiner (B0.1Ti0.7wt%) in the case of lead to Cross electric arc melting production V₉₅Al₅Alloy pig.Do not have the section of the ingot of grain refiner figure 14 illustrates.With crystalline substance Grain fining agent ingot section figure 15 illustrates.Ingot shows two different regions：Crystal grain is perpendicular to ingot surface Cylindrical region；With crystal grain in the region of the equiaxial growth in ingot center.

With the exposed surface of optics microscope photographing, and it is average to be determined according to ASTM E112 to analyze gained image Length intercept.Result is summarised in table 5.

Table 5：Add and without the V of grain refiner₉₅Al₅Crystallite dimension

V₉₅Al₅Alloy has 1069 microns of mean linear intercept.After addition B0.1Ti0.7 (wt%), alloy Mean intercept length in the region with equi-axed crystal be 171 microns, and with columnar grain (perpendicular to crystalline substance Grain the direction of growth) region in be 173 microns.

The method for manufacturing alloy membrane tube

The micro-structural of further refinement casting alloy is needed using alloy of the invention manufacture tubing.Casting and other formation Method produces composition uniform but micro-structural uneven (including porosity) alloy.The machinery of the alloy during tubing manufacture Presence of the failure generally with hole is relevant, and relevant with low elongation, and the low elongation is due to poor micro-structural (uneven distribution of such as crystallite dimension) for causing.It therefore meets it is desirable that with little crystallite size and narrow dimension point Cloth forms the micro-structural of alloy, and makes it have minimum (or minimum) porosity.This micro-structural strengthens alloy Formability, including improve alloy ductility.

Tubing production is multistage method, has the rod of required composition, micro-structural and size including manufacture first, so These rods are deformed into required net shape afterwards.

The refinement of crystallite dimension and bigger micro-structural uniformity are realized with following general program step：

It is V to form solid solution formula_100-(Y+Z)Al_YX_ZVanadium alloy, wherein X=Ti, Cr, Fe, Ni, B；Y For>0~10；And Z is>0~5；And

Formed vanadium is heat-treated at 800 DEG C~1500 DEG C of temperature and the pressure of 50MPa~500MPa to close Gold.

It is then as described below, the vanadium alloy of refining is formed as with pipe deformations method (such as rolling, drawing or extrusion) Tubing.

It is prepared by ingot

The first step is to produce block alloy product, such as ingot with suitable casting method.For laboratory scale method, The ingot 200 of 25mm × 25mm × 100mm is produced with successively electric arc melting.The examination formed by the method Test the example of ingot figure 19 illustrates.It is understood that can be produced by Cold crucible induction melting method that suitable ingot is similar to. This generates the ingot containing hole and larger non-homogeneous grainiess.

Alloy is homogenized

Next step is to minimize to improve the elongation of alloy by the porosity in the ingot by casting, and optimizes downstream tube It is prepared by the micro-structural in manufacture.This realizes that HIP was related within one time of regulation using high temperature insostatic pressing (HIP) (HIP) Apply moderate pressure high simultaneously, thus be used to assign the characteristic needed for the alloy bar of electric arc melting.

Operating parameter for the experimental HIP operations of V-Al alloys is as follows：

1200 DEG C of temperature；

The pressure of 200MPa；

2 hours duration；

The heating/cooling rate of 5k/ minutes；With

Argon atmosphere.

Such as best image in Figure 20 and 21, porosity reduction and crystallite dimension are shown really through the sample of HIP Distribution becomes evenly.Figure 20 provides the light micrograph of the V-Al alloys of HIP before processings, shows Hole 50.Figure 21 provides the light micrograph of the V-Al alloys after HIP treatment.Do not detect obvious Hole.Additionally, compared to cast alloy, the crystallite dimension that experienced refining result in smaller crystallite dimension.

● before HIP treatment, thickness is the casting V of 20mm₉₅Al₅The crystal grain Linear intercept of alloy parallel to It is 15mm on columnar growth direction, is being that 3.6mm (uses ASTM E112-113 methods in the direction of growth Determine), and there is the hole more than 0.3mm.

● after the hip process, same V₉₅Al₅The crystal grain Linear intercept of alloy is 3.0 on parallel to the direction of growth Mm, in the direction of growth for 2.7mm (is determined) with ASTM E112-113 methods, and in the absence of big In the hole of 0.3mm.

Crystal grain Linear intercept from HIP treatment reduces it is anticipated that ductility increase at least 1% can be made, preferably at least 2%, more preferably at least 3%, still more preferably at least 4%, and most preferably at least 5%.Therefore, V-Al of the invention The ductility of alloy is preferably at least 10%, more preferably at least 12%, still more preferably at least 15%.

It has been found that HIP techniques also result in more equiaxial grain shape, it is sliding in more planes due to needing Move and inherently lead to intensity and ductility higher.For purposes of the present invention, in equi-axed crystal shape, growth side To crystal grain Linear intercept and the ratio between the crystal grain Linear intercept perpendicular to the direction of growth be 0.5:1.5 to 1.5:0.5, it is more excellent Elect 0.8 as:1.2 to 1.2:0.8.

Tubular film

Vanadium alloy of the invention is especially suitable for use as the alloy catalytic film of catalytic film reactor (CMR).As described above, closing The composition of gold has been optimized for being formed the tubular film of CMR with the property of thus gained.

Typical CMR 100 is shown in Figure 22, which illustrates water gas converting catalyst 106 and H₂Selectivity The close-coupled of film 108.The schematic diagrames of CMR 100 of diagram show Flat Membrane, wherein CO+H₂+H₂O feeds 101 are fed to reactor shell 104, and catalyst 106 and film 108 are therebetween.Charging 101 is in catalyst 106 It is middle to experience Water gas shift/WGS (WGS) to produce (H of raffinate 110₂The synthesis gas for exhausting) and H₂Penetrant 112.Can also be right Leave the H of film₂102 are purged using optional nitrogen.Used as exothermic reaction, it is have that WGS is reacted in lower temperature Profit, but kinetics is at high temperature favourable.In order to overcome this to limit to, business WGS methods include high temperature Stage (about 450 DEG C, for realizing rapid kinetics, which reduce required reactor size) and cold stage (about 200 DEG C, so that the conversion of the residual CO from hot stage is maximized).CMR is by allowing the WGS high under high temperature Convert and allow to eliminate low-temp reaction device.When the processing of coal derivative synthesis gas is applied to, CMR can be single Almost complete CO to H is realized in device₂Conversion, H₂CO before purification and combustion₂Capture.

Figure 23 shows the prototype tubulose CMR 200 that can include the tubular film formed by vanadium alloy of the invention.Pipe Shape CMR 200 is incorporated with tubular film 208 in tubular shell 204, and catalyst is occupied in housing 204 Annular space.The great advantage of this configuration is that sealing area is reduced, it is only necessary to carried out in each end (such as 214) of pipe close Envelope.Again, CMR 200 produces the (H of raffinate 210₂The synthesis gas for exhausting) and H₂Penetrant 212.Tubulose CMR In view of the bigger utilization to ready-made tubing and compression fitting, this contributes to simple and firm assembling.

The manufacture of tubular film

In view of the sealing area for substantially reducing and simpler construction, tubular configuration provides obvious compared to plane configuration Advantage.When compared with palladium alloy membrane, vanadium class alloy film provides further advantage in the mill.Pd class films must Must be very thin so as to minimization of cost and make hydrogen maximum penetration.This needs to use porous support structures.V class alloys More high osmosis allow using can self-supporting thicker film.This greatly reduce manufacturing process complexity and into This.

Required alloy pipe is desired to have following size：

Diameter (2mm~25mm)；With

Wall thickness (0.05mm~1.00mm).

The manufacture of tubular film utilizes stretcher strain, its material shape size and material character to draw-texture process just like Lower requirement：

- with enough size castings or must be sintered for the preforming material of deformation process, for example, a diameter of 25 Mm~50mm and height for 100mm~300mm cylinder.This to high-melting-point (at most 2000 DEG C), It is significant challenge to need for the V class alloys of high fusing energy, and be result in and becoming that fire resisting encloses that resistance material reacts Gesture；And

- charging should have enough ductilities.It is thought that material of the elongation less than 10% may be not suitable for purport Producing the deformation process of small tubular film.

If meeting above property, can be using the standard production flow of manufacture small size tubular assembly, it includes rod Casting, extrusion and drawing.

The manufacturing process of V-Al (V-1) alloy for being proposed

Based on the property studied, for all V classes alloys studied so far, V-Al alloys are (particularly V₉₅Al₅) there is highest elongation, therefore it is the optimal time that tubular film is manufactured by preferred stretcher strain flow Choosing.

A kind of manufacturing process of V-Al pipes is as follows：

1) produces preformed alloy bar by casting or solid state sintering method, and it has, and 25mm~50mm's is straight Footpath and the length of 50mm~300mm；

2) calcines alloy bar so that ductility reaches maximum；

3) rod is extruded as rough tubing by；

4) by multiple machine processing come the rough tubing of drawing, so as to being made diameter 3/8 with intermediate calcination " and wall thickness≤ The tubular film of 0.2mm；

5) reinforcings heat treatment；And

6) tubing is cut to required length by.

The target size of membrane tube produced by the method is：

- length：≥1000mm；

- external diameter：2mm~25mm, preferably 9.52mm (3/8 ")；With

- wall thickness：0.05mm~1.00mm, preferably≤0.200mm.

Catalytic surface

Alloy film by dissolving-flooding mechanism come work, by this mechanism：

Molecule H₂Adsorb on high pressure surface and split into atomic hydrogen；

Atom H is dissolved in metal and is migrated by being jumped between the interstitial site in metal lattice, and this is by dense Gradient is spent to drive；And

It is H that atomic hydrogen is reconfigured on low-pressure surface₂And desorption.

Vanadium forms the oxide skin(coating) of firm holding, and its catalytic is poor and serves as the barrier of hydrogen dissolving.It is preferred that will catalysis Surface applies to alloy film to realize enough hydrogen molecule dissociative reaction speed with film feed surface.

In order to play a part of film, it is necessary to except oxide described in going, and most notable H must be applied₂Dissociation catalysis The thin layer of agent --- Pd.This area needs to be removed with a series of mechanically and chemically cleanings it is understood that applying Pd layers Oxide, is then deposited on the surface Pd with plating or chemical plating.For the various suitable of these steps Technique is known in the art.

Figure 24 shows the electron micrograph at V-Pd interfaces, it illustrates vanadium 310, palladium coating 312 and asphalt mixtures modified by epoxy resin The hierarchy of fat material for sealing 314.Optimal Pd thickness degree is 200nm~500nm.This Pd thickness degree is carried The good compromise between durability and cost is supplied.

Once the inner surface to selected pipe is applied with Pd layers, then the membrane tube can be used as catalytic film reactor (CMR) In H₂Selective membrane.

Reactor is operated

As it was previously stated, selecting alloy composition of the invention to avoid the phase in version during operation.In this respect, As shown in V-Al phasors, the transition temperature in V-Al alloys is favourable, and it can be used to avoid this phase in version.Compare Under, the transition temperature in V-Ni and V-Cr alloys can not make these alloys required opereating specification (0~500 DEG C, And H/M ratios avoid phase in version more than 0.05) interior.In fact, with the H/M more than 0.05 than from about 400 DEG C When operation temperature is cooled to room temperature, the use of V, V-Ni and V-Cr alloys increased brittle break.This is found in example As shown in Figure 25 to for avoiding V and V₉₀Al₁₀α to β phase in version needed for operation temperature and H/M Comparing.For shutdown, V and other V alloys generally need to purge and the desorption from metal hydrogen before shutdown About 0 is down to by H/M ratios, the temperature in reactor can be then reduced.Therefore, this needs two steps during shutting down Operation.The phase in version of α to β can be avoided during due to using alloy of the invention in normal operation condition, therefore can be kept away Exempt from this hydrogen purge step.

Therefore, provide and can be closed previously for V and other V using the alloy film formed by vanadium alloy of the present invention The advantage of CMR is operated under the conditions of gold is infeasible.Specifically, the alloy film for being formed by vanadium alloy of the present invention can Operated (referring to Figure 25) with the hydrogen more than 0.05 and metal (H/M) ratio and 0~350 DEG C of temperature.

This is particularly advantageous in various operating conditions (including startup and shutdown of reactor) of reactor, because Without the concern for special temperature or H/R when being started and shut down operation in above operating condition.Therefore, this makes instead Answering device can start under the operation temperature of such as 20 DEG C~30 DEG C of room temperature to about such as 200 DEG C~400 DEG C, and Film does not suffer from phase in version.Similarly, this enables reactor in such as 200 DEG C~400 DEG C of operation temperature to for example 20 DEG C~30 DEG C of shutdown at room temperature, and film does not suffer from phase in version.

Therefore, film can be circulated between operation temperature and environment temperature and not suffer from phase in version, so that reactor stops Machine simplifies.

This enables film to be used by multiple operation circulations.The possibility of brittle break is greatly diminished during shutdown.

Using

Main application is in high temperature hydrogen selective synthesizing golden film.These devices are from can also contain H₂O、CO、CO₂、 CH₄And H₂Hydrogen is separated in the mixed airflow of S.One concrete application is to produce H using hydrogen selective synthesizing golden film₂And CO is captured from the coal and biomass of gasification₂。

Other possible applications include the medium for storing high-purity hydrogen, and it is used for portable or distributed power generation Fuel cell, the ionising radiation of aerospace applications are shielded and as thermal energy storage medium.

Those of ordinary skill in the art are readily apparent that method described herein is easy to carry out in addition to those for specifically describing Other variants and modifications.It should be understood that the present invention includes falling the such modification of whole in spirit and scope of the present invention and repaiies Change.

When in this explanation (including claims) using term " including ", "comprising" or when " containing ", it is answered Be read as specifying the feature mentioned by existing, entirety, step or component, but do not exclude the presence of one or more other Feature, entirety, step, component or its combination.

Claims

1. a kind of vanadium alloy, it is included：

Vanadium；

Aluminium, the content of the aluminium is more than 0~10at%；With

The content of Ta, the Ta is less than 0.01at%.

2. vanadium alloy as claimed in claim 1, it is also comprising the crystal grain refinement selected from Ti, Cr, Fe, Ni or B Element, the content of the grain refining element is more than 0~5at%.

3. vanadium alloy as claimed in claim 1, wherein, the ductility of the vanadium alloy is the elongation more than 10% Rate, preferably greater than 11% elongation.

4. vanadium alloy as claimed in claim 1, wherein, the most sample based on 6 crystal grain, preferably 8 crystal grain This amount, the vanadium alloy has the crystal grain Linear intercept less than 5.0mm.

5. vanadium alloy as claimed in claim 1, wherein, the vanadium alloy is more than 0.5mm not comprising average-size Any hole.

6. it is a kind of manufacture vanadium alloy method, it includes：

Form vanadium alloy as claimed in claim 1；And

Formed vanadium alloy is heat-treated at 800 DEG C~1500 DEG C of temperature and the pressure of 50MPa~500MPa,

So as to produce the refining vanadium alloy of the deformation processing suitable for forming light-wall pipe.

7. described in a kind of manufacturing claims 6 refining vanadium alloy method, wherein, refine vanadium alloy ductility It is the elongation more than 10%, preferably greater than or equal to 11% elongation, more preferably greater than or equal to 13% Elongation, the still more preferably elongation more than or equal to 14%.

8. method as claimed in claim 6, wherein, the heat treatment step includes high temperature insostatic pressing (HIP) (HIP) process.

9. method as claimed in claim 6, wherein, the heat treatment step includes experiencing the vanadium alloy 1000 DEG C~1400 DEG C of temperature, is preferably subjected to 1050 DEG C~1380 DEG C of temperature, more preferably experiences at most 1400 DEG C Temperature, even more preferably from about 1200 DEG C of temperature of experience.

10. method as claimed in claim 9, wherein, the heat treatment step includes making the vanadium alloy experience 50 The pressure of MPa~400MPa, preferably 75MPa~350MPa, more preferably from about 200MPa.

11. methods as claimed in claim 9, wherein, the heat treatment step is persistently carried out at least 30 minutes, Preferably at least 45 minutes, more preferably at least 2 hours.

12. methods as claimed in claim 9, wherein, at least one of firing rate or cooling velocity are at least 4K/ minutes, preferably at least 4.5K/ minutes, more preferably 4K/ minutes~10K/ minutes, still more preferably 4K/ Minute~8K/ minutes.

A kind of 13. methods of the tubular film for manufacturing catalytic film reactor, it includes：

Vanadium alloy is formed with the method any one of claim 6~12；And

The vanadium alloy of refining is formed as into light-wall pipe.

14. methods as claimed in claim 13, wherein, the light-wall pipe include external diameter be 2mm~25mm and Wall thickness is the pipe of 0.05mm~1mm.

The film for catalytic film reactor that method described in a kind of 15. use claims 13 is formed.

A kind of 16. methods for operating catalytic film reactor, it includes：

The catalytic film reactor comprising at least one tubular film is provided, the tubular film includes in Claims 1 to 5 Vanadium alloy described in one or with vanadium alloy obtained in the method any one of claim 6~12；And

When the reactor is in 0 DEG C~350 DEG C of operation temperature, with the hydrogen more than 0.05 and metal (H/M) than behaviour Make the catalytic film reactor.

The step of method of 17. operation catalytic film reactors as claimed in claim 16, operation catalytic film reactor Startup process and shutdown operation including the reactor.

The method of 18. operation catalytic film reactors as claimed in claim 16, wherein, the operation temperature is 20 DEG C~300 DEG C.

The method of 19. operation catalytic film reactors as claimed in claim 18, wherein, the H/M ratios are more than 0.1.

The method of 20. operation catalytic film reactors as claimed in claim 19, wherein, operating condition includes described The cooling step of catalytic film reactor, preferably includes catalytic film reactor cooling in the environment.