CN101080265A - Ceramic-metal or metal alloy junction assembly - Google Patents
Ceramic-metal or metal alloy junction assembly Download PDFInfo
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- CN101080265A CN101080265A CNA2005800433793A CN200580043379A CN101080265A CN 101080265 A CN101080265 A CN 101080265A CN A2005800433793 A CNA2005800433793 A CN A2005800433793A CN 200580043379 A CN200580043379 A CN 200580043379A CN 101080265 A CN101080265 A CN 101080265A
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
- C04B35/2641—Compositions containing one or more ferrites of the group comprising rare earth metals and one or more ferrites of the group comprising alkali metals, alkaline earth metals or lead
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- B01D53/34—Chemical or biological purification of waste gases
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- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
- C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
- C04B37/023—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used
- C04B37/025—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used consisting of glass or ceramic material
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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Abstract
The invention concerns a junction assembly (5) comprising: a ceramic tube (3) with axis (X'X), defining an inner zone (ZC) and an outer zone (ZM); a metal socket (2) with cylindrical junction zone (2b) of axis (X'X) enclosing said tube (3) through a gap (4); the sealing between said tube (3) and the socket (2) is provided by a junction element (1), made of a gas-tight material, and having a thermal expansion coefficient higher than 9. 10<-6>/ DEG C; said ceramic having a thermal expansion coefficient higher than that of the metal; said zone (2b) having, perpendicular to (X'X) a small dimension (1). The invention also concerns a reactor (6) comprising such an assembly (5), in particular for gas production and/or for gas separation.
Description
Technical field
The present invention relates to cermet conjugative component and reactor, cermet or metal alloy joint element that described cermet conjugative component comprises ceramic component, metal or metal alloy parts and the joint between described two kinds of parts is provided, described reactor comprises this conjugative component.
Background technology
The metallic reactors that will comprise ceramic membrane for example CMR (catalytic film reactor) be used under the situation of gas generation for example or separation, importantly at pottery with constitute to produce between the metal or metal alloy of wall of described reactor and engage.This is because these reactors generally comprise ceramic component or film in their inside, described ceramic component or film are usually being that the form of hollow pipe exists basically, this hollow pipe end place sealing therein and at other end place opening, pipe fitting partly impales an interior zone, this interior zone comprises a kind of atmosphere that is generally gaseous atmosphere, pipe fitting also divides ground to limit one in the perimeter with respect to pipe fitting self at described inside reactor, and this perimeter comprises that another kind is generally the atmosphere of gaseous atmosphere.Therefore two kinds of atmosphere in the described reactor directly are not communicated with mutually, but are separated by ceramic component.By or pass ceramic component to take place at least a between these two kinds of atmosphere optionally generally be the exchange of gaseous state, this exchange can make a side of described ceramic component that at least a reaction takes place.Pipe fitting generally is held in place in reactor by the parts of being made by metal or metal alloy, and described metal or metal alloy generally is the metal or alloy identical with described reactor wall.Described parts can belong to described wall, perhaps can be attached to simply on the described wall.
In fact, being difficult to technically in a side is that oxidizing atmosphere and opposite side are that pressure differential between reducing atmosphere and the described two kinds of atmosphere is design and produce airtight conjugative component between pottery and the metal or metal alloy under the condition of 0-30 crust (0-0.3Mpa).In addition, using under the situation of CMR, using the condition of this joint even harsher, because described atmosphere is easy to comprise water vapour, and conjugative component must be worked in from about 20 ℃ (room temperatures) to 900 ℃ or higher temperature range.Therefore the requirement for restriction of these associatings uses following material, and no matter described material is pottery, metal or metal alloy or grafting material, all mutual chemical property torpescence, and have suitable physical property, especially suitable TEC (thermal coefficient of expansion).
So far all be limited to two different points, the i.e. form of the prescription of the material of joint element and joint element (design) for the research that produces proper engagement portion.
About the prescription of grafting material, because the parameter of this material changes as time passes and change under high temperature (600-900 ℃), so produce many problems.
In these parameters, most important parameters is material coefficient of thermal expansion coefficient (TEC) and chemistry and physical stability.This is owing in the temperature range from the room temperature to high temperature, must consider possible evaporation, the variation of TEC and/or the possible factors such as crystallization of described material composition of all material compositions as described.In this respect, partly or entirely the material of crystallization has wideer possibility, especially changes all the more so at thermal coefficient of expansion with the variation of temperature and high-temperature durable.
First kind of approach is to make the glass crystallization best as far as possible so that its performance is transferred to, and researched and developed thus by lithium aluminium silicate or LAS type (US4921783), barium silicate aluminium or BAS type (US6430966) or barium silicate calcium aluminium or the formed compound of BCAS type special glass.These compounds and the made glassy phase ratio of common noncrystalline compound have good hear resistance and the TEC of Geng Gao.Regrettably, they demonstrate too high and chemical reactivity pottery.
Second kind of approach be add crystalline phase in the glass increasing TEC, or for example (US5726218 US6402156) uses crystallizable glass with powder or prefabricated component form.Yet, increased the possibility of sewing by the interface expansion that exists several phase to produce in the grafting material, and therefore increased the possibility of conjugative component sealing loss.
About the form of joint element, first kind of approach is that the joint element that will comprise the deformable grafting material compresses, and described element is flattened and pasted the metal or metal alloy parts and pasting ceramic component.Grafting material generally is a for example glass of fluid phase.Thereby it cooperates the shape of described parts.Thereby can make it stand compression stress so that it can its with the interface scope of parts in provide with the good of parts and contact.
Yet shown stress is not minor issue on ceramic component.This is because this stress can make ceramic component crack, and may break when the worst.In addition, in most of the cases, must in joint element, optional feature be set so that airtight fully, especially under the uneven situation of surface state at the interface of joint element and described parts.This layout requires metal or metal alloy parts and ceramic component to have approaching as far as possible thermal coefficient of expansion, because these two parts all closely contact joint element.The possible distortion of metal or metal alloy parts is stress application on ceramic component inevitably.As a rule, thermal cycle repeatedly and/or thermal shock all cause ceramic component to crack.
Second kind of approach is the form that changes joint element, so that restriction may be applied to the stress influence on the ceramic component.Therefore, EP-A2-1067320 has introduced and has a kind ofly formed joint element by at least one spirality metal ring, and described becket can stand distortion.Therefore this joint element can keep the pressure at the interface between described metal or metal alloy parts and the ceramic component.This joint element especially can be limited in the radial stress on the ceramic component that applies during the thermal cycle, because this ring is made by the thickness sheet metal more much smaller than width.On the other hand, because described ring is made of metal, so form the problem that the surface at interface may very fast generation surface roughness, described surface roughness can cause leakage.Here it is why in having the embodiment of at least two rings, inserts and puts the reason of fluid phase (especially glass) usually between two adjacent ring.There is such problem mutually in this fluid, under the promptly described mutually nonliquid therein temperature, especially makes the junction surface hardening from room temperature (about 20 ℃) under the temperature range of the softening temperature of described phase.
Summary of the invention
Can overcome the problems referred to above and introduce other advantage according to conjugative component of the present invention.One of purpose of the present invention provides a kind of conjugative component, and this conjugative component especially limits the stress that is applied on the ceramic component when carrying out thermal cycle under the temperature range from the room temperature to high temperature.
Therefore, the present invention relates to a kind of cermet conjugative component, described assembly comprises:
1) at least one ceramic component, the form of described ceramic component is for having the hollow of axis (X ' X) and being the pipe of cylindricality substantially, this Guan Yiduan sealing and the other end is opened, limit interior zone that is called ceramic region and the perimeter that is referred to as metallic region thus, described ceramic region and metallic region are not interconnected, but separated by ceramic component at least in part, and encapsulate this ceramic component at least in part
2) at least one metal or metal alloy base (socket), this base is called " engaging zones " after comprising and have axis the basic hollow parts one for cylindricality of (X ' X), this part surrounds described pipe at least in part, be arranged on the basic space for annular with axis (X ' X) between described pipe and the described engaging zones
3) provide sealing between described pipe and the described base by at least one cermet joint element, this joint element reaches with pipe and contacts with the engaging zones of described base, this joint element by occupying described annular space the subspace and preferably being that the form of annular element exists and is present at least in part in the described annular space substantially
* described pottery has the thermal coefficient of expansion (TEC) of the thermal coefficient of expansion (TEC) more than or equal to metal or metal alloy,
* described metal alloy comprises by weight at least 10% nickel and at least 15% chromium by weight,
* described joint element comprises at least a grafting material, preferably include described grafting material, described grafting material sealing to gas is provided under 20-900 ℃, under 650-900 ℃ temperature solid preferably, and under the temperature of room temperature to 900 ℃, have more than or equal to 9 * 10
-6/ ℃ and be preferably 9 * 10
-6/ ℃ to 15 * 10
-6/ ℃ thermal coefficient of expansion,
Described conjugative component is designed so that described engaging zones all has small size along passing described engaging zones and any axis vertical with axis (X ' X) (Y ' Y).
In a preferred embodiment of the invention, the ratio along the size of the size of axis (X ' X) and subspace of engaging zones equals 2/1 at least, preferably in the scope of 2/1-100/1.
Engaging zones along the size of axis (X ' X) and subspace along the ratio of the size of axis (X ' X) be meant engaging zones along the average-size of axis (X ' X) and subspace the ratio along the average-size of axis (X ' X).In the back will illustrational situation next wherein subspace and engaging zones all are that described size is the height of ring along the annular of axis (X ' X).
Advantageously, according to the present invention, the combination of the performance of grafting material and the deformability of base makes can realize comparing with the conjugative component of prior art to have improved available conjugative component.These improvement mainly are to show following aspect, i.e. the chemistry of conjugative component and physical stability, restriction be applied to stress on the earthenware, obtain the sealing of gas from the room temperature to high temperature and improve the thermal cycle tolerance of conjugative component with respect to change from the room temperature to high temperature.This is because the existence of the undersized engaging zones of base has advantageously provided the possibility of described base distortion according to the present invention.This distortion is especially limiting the stress that is applied on the earthenware from room temperature (about 20 ℃) in the temperature range of high temperature.
The term sealing of gas " under 20-900 ℃ the temperature to " is interpreted as, and according to the present invention, can not leak gas under 20-900 ℃ temperature.
Term " being solid under 20-900 ℃ temperature " is interpreted as, and according to the present invention, the viscosity of glass is greater than 10
12MPaS, and described temperature is lower than the fusing point of crystal.General and preferably, described grafting material is a solid under the operating temperature of described assembly.
The implication of " thermal coefficient of expansion (TEC) " is known for a person skilled in the art.
Term " small size " is interpreted as, and according to the present invention, is meant that size is less, and be in those skilled in the art can be easily according to the regulation parameter of grafting material for example TEC and base form variation and in the definite size range.Minimum dimension is by the machinability regulation of metal or metal alloy.Undersized example will provide in each example in the back.Usually, described small size is about 20-500 μ m, and preferably about 50-400 μ m is more preferably about 200-300 μ m.
Earthenware generally is the ceramic membrane that is present in the reactor.Base generally is such, be that it can be connected on this reactor by the mode with machinery and sealing removedly or non-removablely, preferably be connected on the wall of reactor, described mechanical system is generally bolt connection, welding or any other sealing assemble method well known by persons skilled in the art.
According to the present invention, pottery generally is an ion conductor, preferentially is the conductor of ion and electronics, and described pottery more preferably comprises at least a lattice, described lattice comprises at least one oxygen hole, and described pottery more preferably is selected from the pottery and the cerium oxide type pottery of calcium titanium type crystal structure.For example, pottery comprises that its composition is respectively La
0.5Sr
0.5Fe
0.9Ti
0.1O
3-δAnd La
0.5Sr
0.4Fe
0.9Ga
3-δPorous layer (being positioned at the ZM side) and compacted zone (being positioned at the ZC side).
The thermal coefficient of expansion (TEC) of pottery generally depends on its prescription.Usually, this coefficient of expansion is 9 * 10
-6/ ℃ to 20 * 10
-6/ ℃.
Preferably, described metal or metal alloy is preferably the layer that comprises on all surfaces one that at least one is made of at least a oxide on the part surface one of described engaging zones, its thickness is generally more than or equal to about 1 μ m, and preferably its thickness is less than or equal to about 10 μ m.Advantageously, the existence of this oxide skin(coating) makes can protect metal or metal alloy during making conjugative component, function bonding between grafting material and the metal or metal alloy especially is provided.If this layer thin excessively (being less than or equal to about 1 μ m usually) then is difficult to engage adhesion between grafting material and the metal or metal alloy.If this layer blocked up (usually more than or equal to about 10 μ m) then exists in the danger of peeling off during the described manufacturing, and therefore do not provide adhesive effect.Concerning every kind of situation, present technique technical staff can both determine the optimum thickness range and/or the optimum thickness of oxide skin(coating) according to the data that he obtained.
Metal can for example be nickel or platinum.Metal alloy generally has following performance: is 8 * 10 with the creep resistance under the interior temperature, fusing point more than or equal to 1200 ℃ and thermal coefficient of expansion (TEC) under 20-900 ℃ with the resistance to reduction under the interior reducing atmosphere, at 1200 ℃ with the non-oxidizability under the interior oxidizing atmosphere, at 1200 ℃ at 1200 ℃
-6/ ℃ to 25 * 10
-6/ ℃ and be preferably 10 * 10
-6/ ℃ to 18 * 10
-6/ ℃.Described alloy generally is selected from special steel, and described special steel for example is a commercial alloy, for example alloy Haynes 230 , alloy HT and alloy Inconel 686 .
Preferably, described grafting material is a glass, described glass have greater than metal or metal alloy thermal coefficient of expansion (TEC) and less than the thermal coefficient of expansion (TEC) of the thermal coefficient of expansion (TEC) of pottery, can stand the pressure reduction of the 0-3Mpa between ceramic region and the metallic region, with respect to pottery chemically is being stable, with respect to metal or metal alloy chemically is being stable, has resistance to reduction at 1200 ℃ under with interior reducing atmosphere, has non-oxidizability at 1200 ℃ under with interior oxidizing atmosphere, can be adhered on the metal or metal alloy and can be adhered on the pottery.
Earthenware generally seals by Any shape such as square or hemispherical or any intermediate shape at one end.In addition, the openend of earthenware can be convenient to be fixed on the base/among shape.
The invention still further relates to the method that is used to make aforesaid assembly, described method comprises following coherent step:
1. to the surface of the engaging zones of small part pre-oxidation metal or metal alloy base or base precursor, so that on described surface, form the layer that at least one is formed by at least a metal oxide at least in part;
2. the precursor of fit engagement material or grafting material, from the base of step 1 and the precursor of ceramic component or this ceramic component, the height place that described assembling generally comprises by making joint element remain on the engaging zones of base wedges, then
3. in inert gas such as nitrogen, the partial pressure of oxygen of 0-22% and under 650-1200 ℃ temperature to carry out 5 minutes to 10 hours heat treatment from the assembly of step 2, comprise that temperature rises from the temperature that room temperature rises to treatment temperature, at least one temperature under treatment temperature is phase fixedly, at least one temperature that drops to stabilization temperature descends, at least one held stationary under stabilization temperature descends with the temperature that at least one reduces the temperature to the treatment temperature terminal at last mutually, the terminal of described treatment temperature generally is a room temperature, and described heat treatment causes forming joint element in conjugative component.
Term " temperature is phase fixedly " is interpreted as, and according to the present invention, described temperature generally keeps the several minutes time to a few hours according to the material that is adopted.
Treatment temperature can be fixed, and perhaps can change in the scope of pointing out.
Described method also can comprise replenish step, and this replenish step is carried out between abovementioned steps 1 and 2 or carried out before step 1, and described replenish step comprises the steps:
The prefabricated component that manufacturing is formed by grafting material, its form is the cylindricality hollow pipe of opening at one end substantially, described manufacturing comprises at least one (at least once) compacting and densified, perhaps at least one sintering, perhaps at least one fusion and in mould, casting, this is manufactured under 600-1200 ℃ the temperature and carried out 10-40 minute, and this prefabricated component is as the precursor (model) of the grafting material of assembling in step 2.
The present invention relates to a kind of reactor at last, described reactor portion within it comprises it at least mainly being according to described conjugative component of the present invention or by making according to method of the present invention, described reactor surrounds this zone ZM, the metal or metal alloy base of conjugative component is connected on the described reactor with mechanical means, and described axis (X ' X) the perpendicular location, described reactor comprises that inlet that at least one is used to make fluid enter regional ZM and at least one are used to make fluid to flow out the outlet of regional ZM, and described reactor comprises that also at least one is used in that fluid enters the inlet of regional ZC and at least one is used to make fluid to flow out the outlet of regional ZC.
In fact or even 1200 ℃ temperature reactor generally must stand the pressure and the temperature from room temperature at least 900 ℃ of 1-30 crust (0.1-3MPa).In addition, this reactor must comprise at least a general metal or metal alloy that can stand reducing atmosphere.
Usually, the selectivity passage of fluid in described reactor is feasible by earthenware between regional ZC and regional ZM, preferably leads to regional ZM from regional ZC.
Preferably, conjugative component is connected on the wall of described reactor with mechanical means.
Usually, described fluid is a gaseous state, and comprises at least a gaseous state composition.
This reactor generally is designed to normally identical with the described base metal or metal alloy that its at least one wall is a metal, perhaps also can be the metal or metal alloy that the metal or metal alloy with base is chemically adapting.
The present invention relates to a kind of method at last, this method is used to utilize described reactor process gas and/or divided gas flow under 400 ℃-900 ℃ operating temperature, and described conjugative component is designed so that grafting material is a solid under the temperature between the operating period of this conjugative component.Usually, when grafting material was glass, operating temperature was less than or equal to the softening temperature of glass.For example, described reactor can be used to utilize methane and oxygen production forming gas.
Operating temperature can change in the said temperature scope or set.In reactor, temperature can distribute unevenly.
Description of drawings
The explanation that provides as non-limitative example below reading by reference accompanying drawing 1-3, the present invention will better understand, and characteristics and advantage will become apparent.In the accompanying drawings:
The schematically illustrated partial view that mainly comprises in it according to the reactor of conjugative component of the present invention of Fig. 1;
The partial view of the schematically illustrated Fig. 1 of Fig. 2 according to conjugative component of the present invention;
Fig. 3 illustrates the thermal cycle that is stood during manufacture according to conjugative component of the present invention with object lesson.
The specific embodiment
The schematically illustrated partial view that mainly comprises in it according to the reactor 6 of conjugative component 5 of the present invention of Fig. 1.Described conjugative component 5 has been welded on the edge in aperture 10 of wall of described reactor 6.Described reactor 6 comprises metal or metal alloy parts or base 2, ceramic component or manages 3 and joint element 1, and described joint element 1 is basic for being coupled to the annular shape in the ringwise substantially space 4 and occupying the basic subspace (4a) for annular that is formed between parts 2 and 3.Described conjugative component 5 and the parts 2,3,1 that form this conjugative component are all coaxial with vertical substantially axis (X ' X) basically.The inside of reactor 6 is divided into two regional ZM and ZC by this device, and described two regional ZM and ZM are in fact mainly by earthenware 3 separately.Conjugative component 5 limits ZC.Reactor 6 and conjugative component 5 localized area ZM.Reactor 6 comprises and is used to the inlet 7 that makes fluid enter regional ZM and is used to make fluid to flow out the outlet 8 of regional ZM.
Produce forming gas (Gaseous Hydrogen H once utilizing reactor 6 to be generally 700-900 ℃ operating temperature in high temperature one
2Mixture with carbon monoxide CO) in the example, air 9 enters regional ZC by entering the mouth, and gaseous methane 7 is sent into regional ZM by entering the mouth, and regional ZM is in the pressure of 30 crust (3MPa).During use, by closing element 1 sealing, oxygen O
2The wall that passes earthenware 3 flows through conjugative component 5.Should pass through with oxonium ion O
2 -Form carry out described oxonium ion O
2 -Via the O in the ceramic lattice
2Pottery is passed in the hole.In regional ZM, then CH can take place
4+ O
2→ H
2The reaction of+CO, described reaction causes generating syngas mixture, and described syngas mixture is discharged by outlet 8.If desired, can be easy to make Gaseous Hydrogen H subsequently
2CO is separated from each other with carbon monoxide.Stay the gaseous nitrogen N among the regional ZC
2By 9 discharges that enter the mouth.
Therefore, can optionally air separation be become gaseous oxygen O
2With gaseous nitrogen N
2, and in the ZM zone of reactor 6, implement and gas reaction as reactant.
The schematically illustrated partial view as shown in Figure 1 of Fig. 2 according to conjugative component 5 of the present invention.
Ceramic component 3 is column tubes of end sealing.This ceramic component 3 also limits ceramic region ZC that is positioned at pipe and the perimeter that is called metallic region ZM.The blind end 3b of pipe 3 is hemispherical and faces base 2.This side is called the top side in the further part of specification.Pipe 3 other end 3a opening also is positioned at the inside of base 2.This side is called the bottom side in the further part of specification.Metallic region ZM and ceramic region ZC directly are not communicated with mutually, and only are the wall connections by earthenware 3.
On the other hand, for upper part, can distinguish two kinds of different configurations.Still in cutaway view, can see that external diameter is along with 45 ° of straight angles of chamfer at 2e place diminish, in the length L scope, external diameter is constant once more then.This external diameter constant portion is engaging zones 2b.The thickness l of engaging zones 2b is according to small size l of the present invention.
As shown in Figure 2, earthenware 3 installs in first recess, and the lower part 3a of this earthenware leans against on the shoulder 2c.By means of shoulder 2a, manage 3 wedges on base 2.
For the vertical axis of the axis of any and the engaging zones 2b that passes base 2 (X ' X) (Y ' Y), described engaging zones 2b has small size l along this axis (Y ' Y).
Joint element 1 is an annular.For this layer, this joint element only occupies the annular subspace 4a of annular space 4.The height of joint element 1 is less than the height L of engaging zones 2b.The degree of depth that joint element 1 inserts base 2 makes its upper part upper end basic and base 2 be in equal height.
Explanation in Fig. 3 example 1 below.
Example
Following example explanation the present invention, but do not limit the scope of the invention.
Example 1
The conjugative component 5 of this example as shown in Figure 2.The size of each parts is as follows:
The width l:0.25mm of engaging zones 2b
The length L of engaging zones 2b: 5mm
The internal diameter of engaging zones 2b: 12mm
The external diameter of part 2e: 12.25-16mm
The internal diameter of part 2e: 12mm
The height of part 2e (along (X ' X)): 5mm
The external diameter of part 2f and 2d: 16mm
The internal diameter of part 2f: 10mm
The height of part 2f: 10mm
The internal diameter of lower part 2d: 7mm
The total height of base 2 (along axis (X ' X)): 50mm
The base 2 of Xian Dinging is the parts (or collar) that are made of alloy Haynes 230 like this.Alloy Haynes is good refractory material, and the reason of selecting this material is its fire resistance, the non-oxidizability under the high temperature and is 15.2 * 10 between room temperature and 800 ℃
-6/ ℃ TEC.(by weight) composed as follows of this material: Ni 57%, and Cr 22%, and Mo 2%, and W 14%, and Fe 3%, and C 0.1%, and Al 0.3%.
Ceramic component 3 is earthenwares 3, the 3b place sealing at one end of this earthenware 3, and on its whole wall, comprise porous layer (being positioned at the ZM side) and compacted zone (being positioned at the ZC side), their composition is respectively La
0.5Sr
0.5Fe
0.9Ti
0.1O
3-δAnd La
0.6Sr
0.4Fe
0.9Ga
0.1O
3-δ, the TEC value that they record between 25-1000 ℃ is identical and equal 14.8 * 10
-6/ ℃, their density is respectively 6g/cm
3And 6.2g/cm
3Porous layer thickness is 0.9mm, and the thickness of compacted zone is 0.1mm.Pipe sizing is:
Length: 252mm
Internal diameter: 0.8mm and
Thickness: 1mm
Grafting material is a glass, and forms joint element 1, and described joint element 1 be substantially in the form of a ring or the parts of band shape 1.This is with 1 to insert fully in the space 4, thereby occupies its subspace (4a), and the top of this band (1) is positioned at the height place at engaging zones 2b top.Test with two kinds of different glass as grafting material.The size of joint element 1 is:
Highly: 25.mm
Inner radial: 0.9mm and
Thickness: 1.4mm.
The ratio along the size of axis (X ' X) of engaging zones 2b and annular subspace 4a equals 5/2.5, promptly equals 2.
Aforesaid conjugative component 5 produced according to the present invention, so that the sealed engagement for gas is provided between earthenware 3 and metal or metal alloy base 2, these conjugative component 5 usefulness glass as grafting material, have cylindrical symmetry axis (X ' X) and show special form (design).Between earthenware 3 inside and outside and therefore apply the pressure reduction of 0-30 crust between two regional ZM of both sides, abutment and ZC, pressure is higher in the ZM side.Be present on two among regional ZM and the ZC atmosphere respectively and therefore be spaced, one of them zone is an oxidizing atmosphere and another zone is a reducing atmosphere.Maximum operation temperature but must provide sealing between room temperature (about 20 ℃) and maximum operating temp between 700-900 ℃.
Described in the first kind of glass PV1 such as U.S. Pat 6430966 that is tested, this glass is easy to crystallization, is about 13 * 10 to form thermal coefficient of expansion
-6/ ℃ and glass transition temperature be 702 ℃ phase.The second kind of glass PV2 that is tested is commercial glass (Schott 8350), and the thermal coefficient of expansion of this glass is 11.7 * 10
-6/ ℃ and glass transition temperature be 521 ℃.The composition of these two kinds of glass is listed in the following table 1, and their physical property that is used in according in the conjugative component 5 of the present invention that is particularly conducive to is listed in the following table 2.
Table 1: the composition of glass PV1 and PV2 (percentage meter by weight)
| PV1 glass | PV2 glass | ||
| Before the crystallization | After the crystallization | ||
| TEC(10 -6/℃) | 11.5 | 12.8 | 11.7 |
| Tg(℃) | 700℃ | - | 521 |
| Tf(℃) | - | 1250℃ | - |
Table 2: the character of glass PV1 and PV2
Under the situation of this example, engage being implemented in of (or sealing) and the following describes.
The preparation of the base made from Haynes 230 alloys 2
The base 2 that makes with Haynes 230 alloys is begun to carry out machined from column, so that obtain as shown in Figure 2 and aforesaid base 2.This column is characterised in that the recess that constitutes engaging zones (thickness), and the glass tape 1 as joint element 1 is housed at the height place of this recess and in inside.The distortion of middle metal or metal alloy advantageously makes it possible to limit thermal stress in this section, and described thermal stress can be applied on the pottery mainly due to the difference of the coefficient of expansion between the material.Free space between shoulder 2a and the glass tape 1 preferably almost completely is full of filler (not shown) herein, so that during engaging heat treatment gas preform is held in place.
Degreasing
| NaOH | 28g/L |
| Tertiary sodium phosphate | 40g/L |
| Sodium carbonate | 20g/L |
| Sodium metasilicate | 20g/L |
| Temperature | 75±5 |
| Incorporation time | |
| 10 minutes |
Table 3: the scheme of preparation saponification solution
Blasting treatment
Subsequently, with diamond dust (Al
2O
3) the engaging zones 2b of described base 2 is carried out blasting treatment, to improve surface roughness, described surface roughness promotes mechanical attachment by making glass infiltrate coarse zone.The roughness Ra that records is about 2.5 μ m.
Peroxidation
By form at metallic surface oxide skin(coating)-be in this case by under 900 ℃, be exposed in the air 30 minutes-further improve and adhere to.By partly being dissolved in the glass, these oxides will provide chemical continuity at the interface in glass/alloy.In order not injure base 2 during the processing of carrying out for manufacturing conjugative component 5, the thickness of oxide skin(coating) must be enough big, but this thickness can not be too big so that can not cause oxide skin(coating) to peel off.
Carry out thermogravimetric analysis so that can determine to form the optimal heat circulation of this oxide skin(coating).
Glass tape 1
Purpose is to form fine and close glass tape 1 between pipe 3 and base 2.
PV1 glass
The form of PV1 glass is a grinding block, described grinding block is carried out single shaft compacting and fires under 700 ℃ air 30 minutes, compacting 15 minutes under 1100 ℃ air then.Resulting tight ness rating is about 98% of solid density.
PV2 glass
The form of PV2 glass is a powder.Directly use this following difficulty that exists: reducing of volume and flowing fast of melten glass between powder that compresses and the melten glass.These two problems can solve by using fine and close gas preform.Single shaft is suppressed described powder and is fired 30 minutes to carry out moulding under 700 ℃ air.Prefabricated component is similar to identical with the external diameter of managing 3 corresponding to its internal diameter and its external diameter is approximate and the identical pipeline section of external diameter of base 2.Resulting tight ness rating is about 98% of solid density after compacting.
The assembling of element
After preparation engages the various elements of usefulness, these elements are assembled together, and during the heat treatment at junction surface, it are held in place.Gas preform-when existing-especially must the remain on height place of the engaging zones 2b of base 2.
At first free space 4 fillings of staying between pipe 3 and the base 2 had chemically inert powder for pottery and alloy.Therefore this filling makes and gas preform can be remained among the engaging zones 2b of base 2.For this reason, also utilize Nextel type (aluminium oxide) fiber that is wound on the pipe 3, should manage wedging base 2.
The material that is used to fill is normally at MgO that chemically is entirely inertia and/or ceramic powders and/or the diamond same with the ceramic phase that constitutes pipe 3 and/or Nextel fiber.
The heat treatment at junction surface
This heat treated purpose is to form ceramic/glass and alloy/glass interface.This stage must be such as nitrogen (N
2) atmosphere inert atmosphere down or under partial pressure of oxygen, carry out so that do not change the composition of pottery.Must control temperature and fixing time mutually fully to avoid making glass breakage.When cooling, the curing of glass may stress application.Must cooling very lentamente under the temperature that is higher than stabilization temperature (perhaps draft temperature).In addition, because glass is solid, and the stress that relates to phase transformation and relate to curing eliminates fully, so can make cooldown rate faster.
PV1 glass
PV1 glass is about 13 * 10 at TEC
-6/ ℃ structure in be easy to crystallization.Purpose is to utilize its flowability, so as before its crystallization with its placed in position and form the interface, thereby increase its TEC (restriction thermal stress) and improve its stability at high temperature.To studies show that of the crystallization of PV1, through after 4 hours, the value of TEC reaches 12.8 * 10 under 850 ℃
-6/ ℃.Analyze at air and the DTA that carries out in nitrogen and to illustrate, have two crystallization peaks, the first crystallization peak appears at 875 ℃, and the second crystallization peak appears at 1000 ℃.
Therefore, heat treatment cycle comprises: fixing 1150 ℃ of following maintenances 15 minutes, fix then at 850 ℃ and keep 4 hours down so that the glass crystallization, then lowering the temperature with the speed cooling of 2 ℃/min, speed with 1 ℃/min between 700 ℃ and 450 ℃ between 850 ℃ and 700 ℃, the speed with 20 ℃/min drops to 20 ℃ then.
PV2 glass
The method of method and PV1 glass is slightly different.Purpose is that glass is scattered to produce ceramic/glass and alloy/glass interface.The viscograph of PV2 glass is known.The softening temperature of this glass is under 715 ℃, and its stabilisation (or annealing) temperature is under 530 ℃.
Thermal cycle as shown in Figure 3, Fig. 3 be temperature T (℃) in time t (hour) pass and the curve that changes.Therefore, this circulation comprises with the speed of 2 ℃/min and heats up, scatters fixing 10 minutes mutually, fast cooling down to the gentle mutually slow cool down of stabilization temperature (530 ℃), held stationary, cool off fast and drop to room temperature then at 750 ℃.
Claims (12)
1. cermet conjugative component (5), described assembly (5) comprising:
1) at least one ceramic component (3), the form of described ceramic component (3) is hollow and is the pipe with axis (X ' X) of column substantially, this the pipe at one end (3b) sealing and at the other end (3a) opening, thereby limit interior zone that is called ceramic region (ZC) and the perimeter that is called metallic region (ZM), described ceramic region (ZC) and metallic region (ZM) are not communicated with mutually and are separated by ceramic component (3) at least in part, and, encapsulate this ceramic component at least in part
2) at least one metal or metal alloy base (2), this base (2) comprises basic for cylindricality and be hollow part (2b), this part (2b) has axis (X ' X) and is called " engaging zones " below, this engaging zones surrounds described pipe (3) at least in part, and be arranged between described pipe (3) and the described engaging zones (2b) and have the basic space (4) of axis (X ' X) for annular
3) sealing between described pipe (3) and the described base (2) is provided by at least one cermet joint element (1), this joint element (1) contacts with pipe (3) and with the described engaging zones (2b) of base (2), this joint element (1) by occupying described annular space (4) subspace (4a) and preferably being that the form of annular element (1) exists and is present at least in part in the described annular space (4) substantially
* the strict thermal coefficient of expansion (TEC) of the thermal coefficient of expansion of described pottery (TEC) greater than metal or metal alloy,
* described metal alloy comprises by weight at least 10% nickel and at least 15% chromium by weight,
* this joint element (1) comprises at least a grafting material, preferably include described grafting material, this joint element (1) provides air-tightness under 20-900 ℃ temperature, be solid under 650-900 ℃ temperature preferably, and has more than or equal to 9 * 10 under the temperature of room temperature to 900 ℃
-6/ ℃ and be preferably 9 * 10
-6/ ℃ to 15 * 10
-6/ ℃ thermal coefficient of expansion (TEC),
Described conjugative component (5) is designed so that described engaging zones (2b) is along passing described engaging zones (2b) and all having small size (l) perpendicular to any axis of described axis (X ' X) (Y ' Y).
2. assembly as claimed in claim 1 is characterized in that, the ratio of engaging zones (2b) size of (X ' X) along the size of described axis (X ' X) and described subspace (4a) along this axis equals 2/1 at least, preferably in the scope of 2/1-100/1.
3. assembly as claimed in claim 1 or 2 is characterized in that, described small size (l) is about 20-500 μ m, is preferably about 50-400 μ m, more preferably about 200-300 μ m.
4. the described assembly of one of claim as described above, it is characterized in that, described pottery is an ion conductor, the conductor of ion and electronics preferably, described pottery more preferably comprises at least a lattice, described lattice comprises at least one oxygen hole, and described pottery is more preferably selected from the pottery of calcium titanium type crystalline texture and cerium oxide type pottery.
5. the described assembly of one of claim as described above, it is characterized in that, described metal or metal alloy preferably comprises the layer that at least one is made of at least a oxide on the part surface of described engaging zones (2b) on all surfaces, the thickness of this layer is more than or equal to about 1 μ m, and preferably is less than or equal to 10 μ m.
6. the described assembly of one of claim as described above, it is characterized in that, described metal or metal alloy have 1200 ℃ with the non-oxidizability under the interior oxidizing atmosphere, 1200 ℃ with the resistance to reduction under the interior reducing atmosphere, 1200 ℃ with the creep resistance under the interior temperature, be greater than or equal to 1200 ℃ fusing point and under 20 ℃-900 ℃ temperature, be 8-25 * 10
-6/ ℃ and preferred 10-18 * 10
-6/ ℃ thermal coefficient of expansion (TEC).
7. the described assembly of one of claim as described above, it is characterized in that, described grafting material is a glass, this glass have greater than metal or metal alloy thermal coefficient of expansion (TEC) and less than the thermal coefficient of expansion (TEC) of the thermal coefficient of expansion (TEC) of pottery, can stand the pressure reduction of the 0-3MPa between ceramic region and the metallic region, with respect to pottery chemically is being stable, with respect to metal or metal alloy chemically is being stable, has resistance to reduction at 1200 ℃ under with interior reducing atmosphere, has non-oxidizability at 1200 ℃ under with interior oxidizing atmosphere, can adhere on the metal or metal alloy and can adhere on the pottery, and preferably have and equal 650 ℃ softening temperature at least.
8. the described assembly of one of claim as described above is characterized in that base (2) comprises that at least one is used to support the shoulder of described pipe (3) (2c) and at least one is used to wedge the shoulder (2a) of described pipe (3).
9. be used for making the method as the described assembly of one of claim 1-8 (5), described method comprises following coherent step:
1) to the surface of the engaging zones (26) of small part pre-oxidation metal or metal alloy base (2) or its precursor, on described surface, to form the layer that at least one is made of at least a metal oxide at least in part;
2) fit engagement material or its precursor, from base (2) and ceramic component (3) or its precursor of step 1, the height place that described assembling generally comprises by the engaging zones (2b) that grafting material is remained on base (2) wedges, then
3) in inert gas such as nitrogen, under the partial pressure of oxygen of 0-22% and under 650-1200 ℃ temperature to carry out 5 minutes to 10 hours heat treatment from the assembly of step 2, comprise from room temperature to the temperature of handling temperature rise, at least one the temperature under the treatment temperature fixedly phase, temperature that at least one drops to stabilization temperature descend, at least one held stationary under stabilization temperature mutually and at least one final temperature that drops to the terminal point of treatment temperature descend, described heat treatment causes formation joint element (1) in conjugative component (5).
10. manufacture method as claimed in claim 9 is characterized in that, also comprises replenish step, this replenish step carry out between the step 1 and 2 of claim 9 or step 1 in claim 9 before carry out, this replenish step is:
The prefabricated component that manufacturing is made by grafting material, the form of this prefabricated component is that opening at one end basic is the hollow pipe of column, described manufacturing comprises at least one compacting and densification steps, perhaps at least one sintering step, perhaps at least one fusion and the step of in mould, casting, this is manufactured under 600-1200 ℃ the temperature and carried out 10-40 minute, and described prefabricated component is as the precursor of the grafting material of assembling in step 2.
11. reactor (6), described reactor (6) portion within it comprises it at least mainly being described or by conjugative component (5) as described in making as claim 9 or 10 described methods as one of claim 1-8, described reactor (6) surrounds described zone (ZM), the metal or metal alloy base (2) of conjugative component (5) is connected with mechanical means with described reactor (6) and the basic perpendicular positioning of described axis (X ' X), described reactor (6) comprises that inlet (7) that at least one is used to make fluid enter regional ZM and at least one are used to make fluid to flow out the outlet (8) of regional ZM, and described reactor (6) comprises that also inlet (9) that at least one is used to make fluid enter regional ZC and at least one are used to make fluid to flow out the outlet (9) of regional ZC.
12. utilize the method for described reactor (6) process gas and/or divided gas flow under 400 ℃-900 ℃ operating temperature, wherein said conjugative component (5) is designed so that grafting material is solid under described operating temperature.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0413533 | 2004-12-17 | ||
| FR0413533A FR2879594B1 (en) | 2004-12-17 | 2004-12-17 | CERAMIC-METAL JUNCTION ASSEMBLY OR METAL ALLOY |
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| Publication Number | Publication Date |
|---|---|
| CN101080265A true CN101080265A (en) | 2007-11-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800433793A Pending CN101080265A (en) | 2004-12-17 | 2005-12-13 | Ceramic-metal or metal alloy junction assembly |
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|---|---|
| EP (1) | EP1827670A1 (en) |
| JP (1) | JP2008524099A (en) |
| CN (1) | CN101080265A (en) |
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| WO (1) | WO2006064160A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104302601A (en) * | 2012-03-12 | 2015-01-21 | 乔治洛德方法研究和开发液化空气有限公司 | Novel ceramic-to-metal seal, and method for producing same |
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|---|---|---|---|---|
| JP2016505501A (en) | 2012-12-19 | 2016-02-25 | プラクスエア・テクノロジー・インコーポレイテッド | Method for sealing an oxygen transport membrane assembly |
| US9212113B2 (en) | 2013-04-26 | 2015-12-15 | Praxair Technology, Inc. | Method and system for producing a synthesis gas using an oxygen transport membrane based reforming system with secondary reforming and auxiliary heat source |
| US9296671B2 (en) | 2013-04-26 | 2016-03-29 | Praxair Technology, Inc. | Method and system for producing methanol using an integrated oxygen transport membrane based reforming system |
| US9938145B2 (en) | 2013-04-26 | 2018-04-10 | Praxair Technology, Inc. | Method and system for adjusting synthesis gas module in an oxygen transport membrane based reforming system |
| RU2680048C2 (en) | 2013-10-07 | 2019-02-14 | Праксайр Текнолоджи, Инк. | Ceramic oxygen transport membrane array reactor and reforming method |
| US10822234B2 (en) | 2014-04-16 | 2020-11-03 | Praxair Technology, Inc. | Method and system for oxygen transport membrane enhanced integrated gasifier combined cycle (IGCC) |
| US10441922B2 (en) | 2015-06-29 | 2019-10-15 | Praxair Technology, Inc. | Dual function composite oxygen transport membrane |
| US10118823B2 (en) | 2015-12-15 | 2018-11-06 | Praxair Technology, Inc. | Method of thermally-stabilizing an oxygen transport membrane-based reforming system |
| US20190002337A1 (en) * | 2015-12-21 | 2019-01-03 | Praxair Technology, Inc. | Apparatus including a ceramic component, a metal component, and a glass sealing material and a process of forming the apparatus |
| US9938146B2 (en) | 2015-12-28 | 2018-04-10 | Praxair Technology, Inc. | High aspect ratio catalytic reactor and catalyst inserts therefor |
| JP2019513081A (en) | 2016-04-01 | 2019-05-23 | プラクスエア・テクノロジー・インコーポレイテッド | Catalyst-containing oxygen transport membrane |
| US10010876B2 (en) | 2016-11-23 | 2018-07-03 | Praxair Technology, Inc. | Catalyst for high temperature steam reforming |
| EP3797085A1 (en) | 2018-05-21 | 2021-03-31 | Praxair Technology, Inc. | Otm syngas panel with gas heated reformer |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE95361C1 (en) * | 1934-08-13 | 1939-04-05 | ||
| GB527580A (en) * | 1938-04-27 | 1940-10-11 | Bosch Gmbh Robert | Improvements in and relating to gas-tight joints between metallic and ceramic insulating bodies |
| FR2592320B1 (en) * | 1985-12-30 | 1988-04-08 | Inst Francais Du Petrole | NOVEL PROCESS FOR OXIDIZING AN OXIDIZABLE CHARGE IN THE GAS PHASE AND REACTOR FOR CARRYING OUT THIS PROCESS. |
| GB9412786D0 (en) * | 1994-06-24 | 1994-08-17 | Johnson Matthey Plc | Improved reformer |
| US6402156B1 (en) * | 1999-04-16 | 2002-06-11 | Eltron Research, Inc. | Glass-ceramic seals for ceramic membrane chemical reactor application |
-
2004
- 2004-12-17 FR FR0413533A patent/FR2879594B1/en not_active Expired - Fee Related
-
2005
- 2005-12-13 JP JP2007546141A patent/JP2008524099A/en active Pending
- 2005-12-13 EP EP05825170A patent/EP1827670A1/en not_active Withdrawn
- 2005-12-13 CN CNA2005800433793A patent/CN101080265A/en active Pending
- 2005-12-13 WO PCT/FR2005/051080 patent/WO2006064160A1/en active Application Filing
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104302601A (en) * | 2012-03-12 | 2015-01-21 | 乔治洛德方法研究和开发液化空气有限公司 | Novel ceramic-to-metal seal, and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1827670A1 (en) | 2007-09-05 |
| WO2006064160A1 (en) | 2006-06-22 |
| JP2008524099A (en) | 2008-07-10 |
| FR2879594B1 (en) | 2007-02-02 |
| FR2879594A1 (en) | 2006-06-23 |
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