JP2020037103A - Conjugate and separation membrane module having the same - Google Patents

Abstract

To provide a conjugate which has high airtightness and excellent durability under high temperature and high pressure conditions when manufacturing a conjugate comprising a complex of zeolite and inorganic porous support, which is a separation membrane, and a dense component.SOLUTION: When manufacturing a conjugate in which a complex of zeolite and inorganic porous support, and a dense component are conjugated with inorganic glass, a metallic component is used as the dense component, and a specific inorganic glass, of which a thermal expansion coefficient is 30×10/K or more and 90×10/K or less and a softening point is 550°C or less, is used, whereby damage received by zeolite when bonding is reduced, and a conjugate, which has high airtightness and sufficient durability under high temperature and high pressure conditions, can be provided.SELECTED DRAWING: None

Description

  The present invention relates to a joined body and a separation membrane module having the same.

Usually, a membrane having gas separation ability is formed on an inorganic porous support and then used by being bonded to a dense member through which gas does not pass. At that time, it is necessary to join in a highly airtight state. Conjugate joined in Patent Document 1 and the metal of the gas separation membrane and the metal member is a glass thermal expansion coefficient of ^{50 × 10 -7 / K~80 × 10} -7 / K is disclosed. Further, Patent Document 2 discloses that a zeolite membrane and an alumina gas conduit can be joined by using a separation glass sealing composition comprising a specific glass containing predetermined amounts of B ₂ O ₃ and PbO and alumina. That is, conventionally, in consideration of the coefficient of thermal expansion, a metal member is generally used in the case of a metal separation membrane, and a dense ceramic member is used in the case of using a ceramic support. Further, Patent Document 3, the ceramic member and the Fe-Ni-Co alloy member and the thermal expansion coefficient of sealing glass of ^{55 × 10 -7 / K~65 × 10} -7 / K structure is disclosed I have.

  Here, when a zeolite membrane is used as the membrane having gas separation ability, treatment at a high temperature is not preferable because there is a concern about heat resistance of the zeolite membrane. According to Patent Literatures 1 and 3, the treatment of joining at a high temperature of 900 ° C. or more may cause structural deterioration such as breakage of the zeolite membrane, and may cause deterioration of separation performance. In addition, joining at a high temperature not only requires time for heating and cooling, but also damages the joint itself due to temperature changes, affecting the performance and life of separation as a joined body. Leads to a decrease in efficiency and an increase in cost in mass production of

  On the other hand, it is necessary that the joined body obtained by joining the separation membranes has sufficient airtightness and can withstand a use temperature and a use pressure for a long time. However, conventional joints were not satisfactory in these respects. For example, a joined body in which ceramics such as alumina as disclosed in Patent Document 2 is joined to a separation membrane has insufficient strength and durability. In particular, when used under a high temperature and a high pressure for a long period of time, factors such as vibration caused by contact with a fluid are superimposed to cause cracks and even breakage.

Public information of JP-A-7-163827 JP 10-180060 PR JP 2013-203602 PR

  The present invention provides a bonded body in which a composite of a zeolite and an inorganic porous support and a dense member are bonded, realizing high airtightness, and substantially eliminating the damage of the zeolite during bonding. It is another object of the present invention to further improve durability under high-temperature and high-pressure conditions.

The present inventors have conducted intensive research, and in order to join the composite of zeolite and the inorganic porous support to the dense member without excess or shortage, the dense member is made of a metal member, and a specific heat is used. The inventors have found that the above-mentioned problems can be solved by joining with a glass having an expansion coefficient and a softening point, and have reached the present invention. The present invention includes the following.

<1> A bonded body in which a composite of zeolite and an inorganic porous support is bonded to a dense member via an inorganic glass, wherein the dense member is a metal member, and the thermal expansion coefficient of the inorganic glass is A joined body having a ^{hardness of} 30 × 10 ⁻⁷ / K or more and 90 × 10 ⁻⁷ / K or less and a softening point of 550 ° C. or less.
<2> The joined body according to <1>, wherein a joint portion between the composite and the dense member is covered with a sealing film.
<3> The joined body according to <2>, wherein the sealing film is a silica film.
<4> The joined body according to any one of <1> to <3>, wherein the inorganic glass contains SnO and / or B ₂ O ₃ .
<5> The joined body according to any one of <1> to <4>, wherein the dense member has a coefficient of thermal expansion of 30 × 10 ⁻⁷ / K or more and 200 × 10 ⁻⁷ / K or less.
<6> A method of using the joined body, wherein the joined body according to any one of <1> to <5> is used under a high temperature condition of 100 ° C to 500 ° C and / or a high pressure condition of 0.5 to 10 MPa.
<7> A separation membrane module having the joined body according to any one of <1> to <5>.
<8> A reactor having the separation membrane module according to <7>.
<9> A joining method for joining a composite of zeolite and an inorganic porous support and a dense member using an inorganic glass, wherein the dense member is a metal member, and the thermal expansion coefficient of the inorganic glass is Is 30 × 10 ⁻⁷ / K or more and 90 × 10 ⁻⁷ / K or less, and the softening point is 550 ° C. or less.

  According to the present invention, a composite of zeolite and an inorganic porous support, which is a separation membrane, and a dense member are produced when a bonded body is produced.When the dense member is a metal member, a specific inorganic glass is used as a glass-based adhesive. By using, it is possible to reduce the damage to the zeolite at the time of bonding, and to provide a joined body having high airtightness and sufficient durability under high temperature and high pressure conditions.

FIG. 2 is a schematic cross-sectional view of a joined body in which a composite of zeolite and an inorganic porous support and a dense member are joined with inorganic glass. FIG. 2 is a schematic cross-sectional view of a joined body in which a composite of zeolite and an inorganic porous support and a dense member are joined with inorganic glass. FIG. 2 is a schematic cross-sectional view of a joined body in which a composite of zeolite and an inorganic porous support and a dense member are joined with inorganic glass.

  Hereinafter, the present invention will be described in detail. However, the description of the constituent requirements described below is an example (representative example) of the embodiment of the present invention, and the present invention is not limited to these contents. Various modifications can be made within the scope of the gist.

<Zeolite>
The main zeolite constituting the zeolite membrane preferably contains a zeolite having a pore structure of 12 or less oxygen rings and 6 or more oxygen rings, and a zeolite having a pore structure of 10 or less oxygen rings and 6 or more oxygen rings. Are more preferable.
Here, the value of n of the zeolite having an oxygen n-membered ring is such that the number of oxygen is the largest among pores formed of oxygen forming the zeolite skeleton and T element (element other than oxygen forming the skeleton). Show things. For example, when pores having a 12-membered oxygen ring and an 8-membered ring exist as in a MOR-type zeolite, it is regarded as a zeolite having a 12-membered oxygen ring.

The zeolite having a pore structure of 12 or less oxygen rings and 6 or more oxygen rings is a code defined by International Zeolite Association (IZA), for example, AEI, AEL, AFI, AFG, ANA, ATO, BEA, BRE, CAS, CDO, CHA, CON, DDR, DOH, EAB, EPI, ERI, ESV, EUO, FAR, FAU, FER, FRA, HEU, GIS, GIU, GME, GOO, ITE, KFI, LEV, LIO, LOS, LTA, LTL, LTN, MAR, MEP, MER, MEL, MFI, MON, MOR, MSO, MTF, MTN, MTW, MWW, NON, NES, OFF, PAU, PHI, RHO, RTE, RTH, RUT, SGT, SOD, STI, STT, TOL, ON, TSC, UFI, VNI, WEI, such as YUG, and the like. It is preferably one selected from these.
In addition, the present invention is particularly preferably used because zeolite is selectively adsorbed, is not a simple molecular sieve, i.e., simply because of the difference in the size of the molecule, but not as a sieve, but is selectively adsorbed. More preferably, it can be used for the purpose of allowing the larger molecule to permeate or separating those having the same size. That is, it is more preferable that the zeolite be separated by selective adsorption on the surface of the zeolite. In such a zeolite, when the temperature is increased, its selective adsorption ability is weakened, so that the effect of the present invention is more remarkably exhibited.

<Inorganic porous support>
Since zeolite has poor plasticity, when it is formed into a film, it is produced while being supported on some substrate. The support is porous so that gas molecules can enter, and has, for example, a large number of fine pores continuous in a three-dimensional shape.

In the present embodiment, the material constituting the support is preferably chemically stable, in which the gas to be treated does not react, and excellent in mechanical strength, specifically, various types of alumina and silica. , Silica-alumina, mullite, cordierite, zirconia, and oxide ceramics, as well as silicon carbide, carbon, and glass.
The shape of the support varies depending on the use of the zeolite membrane. Particularly, the zeolite membrane on the cylindrical support has high strength against external pressure, and is used in a batch process, a distribution process (including a recycling process), and the like. It is suitable for simple use.

<Composite of zeolite and inorganic porous support>
In the present embodiment, for example, a cylindrical support is prepared, and first, microcrystals of zeolite are supported in pores. A dipping method, a rubbing method, a suction method, an impregnation method, or the like can be used as a method for carrying the particles. The microcrystal serves as a nucleus when growing a crystal constituting the zeolite membrane, and is also referred to as a seed crystal. In the zeolite growth step, hydrothermal synthesis can be used as in the case of zeolite synthesis.
The thickness of the zeolite membrane in the zeolite membrane composite is not particularly limited, but is usually 0.1 μm or more, preferably 0.5 μm or more, and is usually 50 μm or less, preferably 20 μm or less. By setting the film thickness to an appropriate thickness, denseness can be maintained and high film selectivity can be maintained. Further, the gas to be taken out can be sufficiently transmitted without increasing the pressure more than necessary.
When the substrate has a tubular shape, the surface coated with zeolite may be on the outside, inside or both of the tubes.
In the process up to the growth of zeolite crystals on the support, a batch process can be performed with both ends of the support open.

<Dense components>
The dense member is used to take out the separated gas to the outside, for example, a tube, and has a degree of denseness (confidentiality) such that the gas to be treated does not leak from the member. In the present invention, a metal member is used. Examples of the metal mentioned here are preferably those having both heat resistance and corrosion resistance, such as a SUS material made of stainless steel, a nickel-molybdenum-iron alloy (for example, Hastelloy (registered trademark)), and inconel (a nickel-chromium-iron alloy). ), Copper, copper alloys (brass, copper, cupronickel), aluminum, aluminum alloys, titanium and the like, and particularly preferably Kovar (iron-cobalt-nickel alloy).
The thermal expansion coefficient of the dense member is usually 30 × 10 ⁻⁷ / K or more and 200 × 10 ⁻⁷ / K or less, and the lower limit is preferably 35 × 10 ⁻⁷ / K or more, and more preferably 40 × 10 ⁻⁷ / K or more. It is more preferably 45 × 10 ⁻⁷ / K or more. The upper limit is preferably 150 × 10 ⁻⁷ / K or less, more preferably 120 × 10 ⁻⁷ / K or less, and even more preferably 85 × 10 ⁻⁷ / K or less. When the coefficient of thermal expansion of the dense member is in the above range, the difference from the coefficient of thermal expansion of the inorganic glass is smaller, and good airtightness and durability can be maintained.
In the present invention, the coefficient of thermal expansion refers to a coefficient of linear expansion, and indicates a rate of change in the length direction of a solid caused by a rise in temperature. It is carried out according to the method described in JIS Z 2285 (metal material), JIS R 1618 (ceramics) and the like. The coefficient of thermal expansion is usually measured in a range where the change in length is proportional to a change in temperature. In this specification, the coefficient of thermal expansion is a value usually measured at 30 to 250 ° C.

<Inorganic glass>
The inorganic glass according to the present embodiment has a thermal expansion coefficient of usually 30 × 10 ⁻⁷ / K or more, preferably 40 × 10 ⁻⁷ / K or more, more preferably 45 × 10 ⁻⁷ / K or more. It is usually at most 90 × 10 ⁻⁷ / K, preferably at most 80 × 10 ⁻⁷ / K, more preferably at most 75 × 10 ⁻⁷ / K.

In the present embodiment, the thermal expansion coefficient of the inorganic glass is usually 60% or more, preferably 70% or more, more preferably 80% or more of the thermal expansion coefficient of the dense member, and is usually 200% or less, preferably 150% or more. %, More preferably 120% or less. When the thermal expansion coefficient of the inorganic glass is equal to or less than the above upper limit, when the temperature is lowered after joining at a temperature at which the inorganic glass melts, internal stress is less likely to occur around the joined portion, and cracks at the joined portion are reduced. Is suppressed. On the other hand, since the coefficient of thermal expansion of the glass is equal to or more than the lower limit, a gap is hardly generated between the composite and the dense member in the operating temperature range of the joined body, and the separation target gas flows from the gap to the purified gas side. Leakage can be suppressed.
The bonded body thus obtained preferably has an air permeation amount after bonding of 10 sccm or less, more preferably 8 sccm or less, in the test method described in the section of Examples of the present specification, Most preferably, it is 5 sccm or less.
Further, the joined body after joining was added with 1/16 by volume of methanol and 1/16 of demineralized water with respect to the internal volume in an autoclave, and the temperature was raised to 280 ° C. in one hour. After maintaining for a period of time, the mixture is naturally cooled, dried at normal pressure at 120 ° C. for 4 hours, and even if the air permeation amount is measured again, the air permeation amount is preferably 10 sccm or less, more preferably 8 sccm or less. Most preferably, it is 5 sccm or less. By satisfying such a condition in addition to the condition of the coefficient of thermal expansion, even if the production of methanol is performed for a longer time, there is no problem in the joint portion, so that it is more preferable.

  When the separation module having the joined body according to the present embodiment is used industrially, the separation module may be reciprocated many times between room temperature and the use temperature, and may be operated for a long time at the use temperature. is there. Therefore, it is required that the gas to be separated does not leak even under these high-temperature and high-pressure conditions at the joint formed by the inorganic glass. By setting the thermal expansion coefficient of the inorganic glass as described above, Leakage of the target gas can be suppressed.

  The inorganic glass according to the present embodiment has a softening point of 550 ° C or lower, preferably 530 ° C or lower, more preferably 480 ° C or lower. Generally, glass frit of inorganic glass can be made to flow by baking at a temperature about 50 ° C. higher than the softening point. Therefore, by setting the softening point of the inorganic glass within the above range, the zeolite and the inorganic glass can be chemically bonded at a relatively low temperature of about 600 ° C. or lower, and the inorganic The glass enters, and the composite and the dense member can be mechanically and strongly joined. Further, by setting the joining temperature to a relatively low temperature, it is possible to reduce the damage to the zeolite due to heating during joining. In addition, by performing the bonding itself at a low temperature, it is possible to reduce damage at the time of cooling the bonded portion, and it is expected that the characteristics are improved and the life is extended.

The inorganic glass is not particularly limited as long as it has the above-mentioned coefficient of thermal expansion and softening point. Examples of the components contained in the inorganic glass include SiO ₂ , Al ₂ O ₃ , ZnO, P ₂ O ₅ , Bi ₂ O ₃ , BaO, TiO ₂ , TeO ₂ , V ₂ O ₅ , B ₂ O ₃ , and SnO. , PbO and the like. Among these, it is particularly preferable to contain B ₂ O ₃ and / or SnO from the viewpoint of improving airtightness. The B ₂ O ₃ and / or inorganic glass containing SnO, specifically, _SnO-P 2 _{O 5} based _glass, Bi ₂ O 3 -ZnO based _{glass, Bi 2 O 3 -B 2 O} 3 based glass, _{Bi 2 O 3 -B 2 O 3} -SiO 2 based _{glass, Bi 2 O 3 -ZnO-B} 2 O 3 type glass, and the like. Commercially available glass frit of such inorganic glass includes “FP-74”, “KP312E”, “FP-67”, “BNL115BB”, “ASF-1094”, “ASF-1098”, “ASF-1109”. (Manufactured by AGC); "BF-0606", "BF-0901" (manufactured by Nippon Electric Glass) and the like.

When the inorganic glass contains SnO, its content is not particularly limited, but is usually 80% by mass or less, preferably 75% by mass or less, more preferably 70% by mass or less, and usually 10% by mass or less, preferably Is at least 20% by mass, more preferably at least 30% by mass.
By setting the SnO content within this range, the fluidity of the glass is sufficiently maintained, and sufficient airtightness is easily obtained. The details of the effect of adding SnO are unknown, but it is known that SnO acts as a reducing agent, and thus the oxide film on the surface of the dense member is modified or the thickness of the oxide film increases during the bonding process. It is speculated that this has led to improved airtightness.

On the other hand, when the inorganic glass contains B ₂ O ₃ , the content is usually 25% by mass or less, preferably 20% by mass or less, more preferably 18% by mass or less, and further preferably 15% by mass or less. . Further, it is usually at most 1% by mass, preferably at least 2% by mass, more preferably at least 3% by mass.
By adding B ₂ O ₃ , the wettability with the dense member is improved, and the airtightness is easily improved. On the other hand, if the content of B ₂ O ₃ is large, the softening point tends to increase, and the degree of freedom of mixing other components is reduced in order to reduce the softening point to 550 ° C. or lower. Therefore, it is preferable to select from the above range. . In addition, since B ₂ O ₃ is soluble in water and alcohol, when there is a possibility of exposure to these substances under high-temperature or high-pressure conditions, it is preferable that the above-mentioned upper limit value or less be used.

The methods for quantifying the contents of SnO and B ₂ O ₃ include XRF (X-ray fluorescence analysis), ICP (Inductively Coupled Plasma Emission Spectroscopy), and the like.

  There is no particular limitation on the form of the inorganic glass, and powdered glass frit, a tablet obtained by molding a glass frit by tableting, a tablet obtained by sintering a glass frit, an organic solvent or a glass frit. A glass paste or the like uniformly dispersed in a binder can be used. When a large number of joined bodies are produced, a tablet or a paste is particularly preferable among these, because it leads to an improvement in production efficiency.

In the present embodiment, the inorganic glass preferably has a lead (Pb) content of 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, even more preferably 2% by mass in terms of PbO. %, Particularly preferably 1% by weight or less, most preferably 0% by weight of inorganic glass.
The lead content can also be measured by XRF (X-ray fluorescence analysis), ICP (Inductively Coupled Plasma Emission Spectroscopy) or the like.

<Joint of a composite of zeolite and inorganic porous support and dense member>
In this embodiment, when the composite is a cylindrical support, the bonding may be performed at both ends. For example, when performing a mixed gas separation process using a zeolite membrane in which the composite is cylindrical, the outside of the cylindrical support having the zeolite membrane is filled with the mixed gas and pressure is applied, or the inside is evacuated. Performs the separation. Therefore, one end may be sealed with a cap and a pipe may be connected to the other end, or a pipe may be connected to both ends.

  A method of joining a composite having a zeolite membrane on its surface and a cap made of a dense member, or a pipe made of a dense member having a terminal structure similar to the cap, is a method that can join the composite and the cap with inorganic glass. Any method may be used, for example, filling the concave portion of the dense member with inorganic glass, placing a composite having a zeolite membrane on the surface thereon, and then placing a weight on the upper portion of the composite to apply a load. And a method of bonding by baking in a state of being heated.

  It is essential that the firing temperature at the time of joining the composite and the dense member with the inorganic glass be higher than the softening point of the inorganic glass used. Therefore, the firing temperature is usually at least the softening point plus 10 ° C., preferably at least the softening point plus 30 ° C., more preferably at least the softening point plus 50 ° C. In order to avoid thermal damage to the zeolite membrane, the temperature is usually 600 ° C. or lower, preferably 580 ° C. or lower, more preferably 560 ° C. or lower. The firing time of the bonding is usually 5 minutes to 90 minutes after reaching the firing temperature, preferably 10 minutes or more, more preferably 20 minutes or more, preferably 60 minutes or less, and more preferably 40 minutes or less.

An example in which a composite of zeolite and an inorganic porous support and a dense member are joined via an inorganic glass will be described below with reference to FIGS.
As shown in FIG. 1, a composite 1 of zeolite and an inorganic porous support and a flange 2 can be directly joined via an inorganic glass 4. In such an embodiment, it is possible to reduce a risk such as gas leakage due to the deterioration of the connection between members over time. In this case, the flange 2 is a dense member made of a metal member.
On the other hand, as shown in FIG. 2, the composite 1 of zeolite and the inorganic porous support and the pipe 3 may be simply joined via the inorganic glass 4. Since the inorganic glass of this embodiment has high airtightness and durability, such bonding is also possible. In this case, the pipe 3 is a dense member made of a metal member.
FIG. 3 is a schematic cross-sectional view showing an example in which a composite 1 of zeolite and an inorganic porous support and a pipe 3 are joined via an inorganic glass 4. The composite 1 of zeolite and the inorganic porous support is joined to the pipe 3 via the inorganic glass 4. The pipe 3 is joined so as to cover the composite 1 of zeolite and the inorganic porous support.

<Sealing coating>
In this embodiment, it is preferable that the joint between the composite and the dense member is covered with a sealing film. In the joint portion, micro holes such as micro cracks and pinholes may be formed on the surface of the joint portion due to baking for curing the inorganic glass used for the joint. Therefore, it is preferable from the viewpoint of improving the airtightness that a sealing process is performed on the joint portion to close these fine holes. In addition, it is preferable that the joint portion is covered with the sealing film also in that the sealing film formed by the sealing treatment can suppress deterioration of the joint portion and damage such as pinholes.

Examples of the sealing agent capable of forming the sealing film include those containing an inorganic material such as silica and various aluminas; organic polymers such as a silicone resin, an epoxy resin, and a fluorine-based resin; And may be solventless. In the present embodiment, it is preferable to use an inorganic sealing agent, particularly silica, from the viewpoint of adhesion to inorganic glass and gas barrier properties. The amount of the sealing agent to be applied may be appropriately determined according to the desired film thickness of the sealing film.
The viscosity is preferably 2 (mPa · s, 25 ° C.) or more, more preferably 5 (mPa · s, 25 ° C.) or more, and still more preferably 10 (mPa · s), from the viewpoint of the handleability of the sealing agent, and particularly the prevention of dripping. s, 25 ° C) or higher. In addition, from the viewpoint that the sealing agent easily penetrates into the pores, 200 (mPa · s, 25 ° C) or less, preferably 100 (mPa · s, 25 ° C) or less, more preferably 50 (mPa · s, 25 ° C). It is as follows. By setting the content in this range, the airtightness is improved, and the handleability is also excellent.

  As a specific sealing method, first, a sealing agent is applied to the joint portion, and is applied by spraying or the like to obtain a coating film. At this time, for the purpose of improving the airtightness, the pressure may be reduced on the opposite side of the joint portion where the sealing agent is adhered. The decompression may be performed before the sealing agent is adhered to the surface of the joined body, may be performed simultaneously with the adhesion, or may be performed after the adhesion. Due to such reduced pressure, the sealing agent can penetrate into the pores of the joint without any gap, thereby closing the pores on the surface of the joint.

  Next, the obtained coating film is cured to form a sealing film. As a curing method, an appropriate method may be employed depending on the type of the sealing agent. When a solution of a polymer material or a suspension of inorganic fine particles is used as the sealing agent, the composition may be dried at 100 to 300 ° C. for 60 to 300 minutes, and the composition containing the polymer material and the crosslinking agent may be used. When used, heat curing, light curing and the like may be performed. When an organic or inorganic monomer or oligomer is used as the sealing agent, it may be cured by polymerizing them at 100 to 300 ° C. for 30 to 180 minutes.

When a silica coating is used as the sealing coating, a sealing treatment called a silicate oligomer treatment can be performed. The silicate oligomer treatment is performed, for example, as follows. First, a sealing agent containing a silicate oligomer represented by an alkoxysilane compound is applied to the joint. Commercial products of such a silicate oligomer include MKC silicate (registered trademark) MS-51, MS-56, MS-57, and MS-56S (all manufactured by Mitsubishi Chemical Corporation, methyl silicate oligomer), ethyl silicate 40, ethyl Examples thereof include silicate 48 (all manufactured by Colcoat, ethyl silicate oligomer), silicate 40, silicate 45 (Tama Chemical Industry), and EMS-485 (manufactured by Colcoat) which is a mixed oligomer of methyl silicate and ethyl silicate. Next, the obtained coating film is heated at 150 to 280 ° C. for 30 to 180 minutes, and a hydrolysis and polycondensation reaction by a sol-gel method is performed to obtain a silica coating.
When a silicone resin is used as the sealing film, a sealing agent containing an alkoxyalkylsilane oligomer may be used. Examples of such sealing agents include Permeate HS-80, HS-90, HS-100, HS-200, HS-300, HS-330, HS-350, HS-360, and HS-820 (all And D Corp.). The silicone resin film is obtained by heating the coating film obtained by applying these at 100 ° C. to 250 ° C. for 30 minutes to 180 minutes.

<Separation membrane module>
A separation membrane module according to another embodiment includes a composite of zeolite and an inorganic porous support and a dense member, and may further include a container having an inlet and an outlet, a flange, a pipe, and the like.
The separation membrane module can separate gases and solvents by installing it in a high-pressure vessel and applying pressure, or by evacuating the permeate side. Further, the separation membrane module may be used in a form that separates simultaneously with the reaction.

<Reactor>
By installing the separation membrane module of this embodiment in a reactor, a product and / or by-product is extracted from the reactor in a production method utilizing a reaction that may cause a reverse reaction, so that a product is collected. The rate is improved, and there is little possibility of breakage and the like, and it can be used for a long time.

<Use conditions>
When the joined body of this embodiment is used in a chemical reaction process, the temperature is usually 100 to 450 ° C, preferably 200 to 350 ° C. It can be used under high temperature conditions of 150 ° C to 500 ° C. The pressure is usually 0.5 to 8 MPa, preferably 2 to 6 MPa. It can be used under high pressure conditions of 0.5 to 10 MPa.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless departing from the gist of the present invention. Various measurements and evaluations in the examples were performed as follows.

<Coefficient of thermal expansion of inorganic glass and dense member>
The coefficient of thermal expansion (linear expansion coefficient) of the glass frit of inorganic glass and the dense member at 30 to 250 ° C. is determined by preparing a cylindrical test piece having a diameter of about 5 mm and a length of about 10 to 20 mm from a sample, and performing a test in the above temperature range. The amount of expansion of the piece is measured with a differential thermal dilatometer (TMA8310, manufactured by Rigaku Corporation), and the average linear expansion coefficient is calculated. In this example, catalog values or values from the manufacturer's report were used.

<Softening point of inorganic glass>
The softening point is measured with a differential thermal analyzer (TG8120, manufactured by Rigaku Corporation). The glass frit ground in a mortar is heated at a rate of 10 ° C./min, and the second inflection point of the obtained DTA curve is defined as a softening point.
In addition, the value of this Example described the value of a catalog or a maker report.

<Air permeability measurement>
Under atmospheric pressure, the end of the joined body (the side to which the cap was not joined) was connected to a 5 kPa vacuum line while maintaining airtightness, and the zeolite membrane was placed using a mass flow meter installed between the vacuum line and the joined body. The flow rate of air passing through the composite was measured. In addition, sccm represents cc / min in terms of 0 ° C. and 1 atm. As a mass flow meter, GF40 (maximum flow rate 20 sccm) manufactured by Brooks Instruments was used.

<Durability test>
The conjugate obtained in the example and the comparative example was put into the SUS-316 autoclave having an inner volume of 80 ml, and 5 ml of methanol and 5 ml of demineralized water were further added. The temperature was increased to 1 ° C. by heating for 1 hour. At this time, the pressure inside the autoclave was 3.5 MPa. 48 hours after the temperature reached 280 ° C., the heating was terminated, and the autoclave was taken out of the electric furnace and allowed to cool naturally. After cooling for 2 hours or more, the autoclave was opened and the joined body was taken out. After drying this at 120 ° C. for 4 hours at normal pressure, the above-mentioned measurement of the amount of air permeation was carried out.

<Example 1>
(Preparation of composite of zeolite and porous alumina support)
A cylindrical alumina porous support (outer diameter: 12 mm, inner diameter: 9 mm, overall length: 40 mm) to which a seed crystal was previously attached was prepared using a composition (molar ratio) of SiO ₂ : Na ₂ O: Al ₂ O ₃ : H ₂ O = 100. : 27.8: 0.021: 4000, vertically immersed in a Teflon (registered trademark) inner cylinder containing an aqueous reaction mixture, the autoclave was sealed, and hydrothermal synthesis was performed at 180 ° C. for 12 hours. After elapse of a predetermined time, the mixture is allowed to cool to room temperature, the porous support-zeolite composite is taken out of the reaction mixture, washed, and dried at 120 ° C. for 4 hours or more to form a composite of the MFI zeolite and the alumina porous support. I got a body.

(Preparation of bonded body)
AGC glass frit “FP-74” (coefficient of thermal expansion) as an inorganic glass in a concave portion of a cap made of Kovar (coefficient of thermal expansion 52 × 10 ⁻⁷ / K, outer diameter 14.0 mm, inner diameter 12.2 mm, height 4 mm) 0.3 × 10 ⁻⁷ / K, softening point: 355 ° C., SnO content: 42%), and the composite of the MFI-type zeolite and the alumina porous support was placed thereon. Then, a 560 g weight was placed on the upper part of the composite and placed in a muffle furnace with a load applied thereto. The temperature was raised to 480 ° C. over 100 minutes, and then the state of 480 ° C. was maintained for 30 minutes and fired. After that, the heating was stopped, and natural cooling was performed to obtain a joined body.

  About the obtained joined body, the air permeation amount measurement and the durability test were performed. As a result, the air permeability of the joined body before the durability test was 0.1 sccm or less. In addition, the air permeation amount of the joined body after the durability test was 0.1 sccm or less, which was the same before and after the test, indicating that good durability was exhibited.

<Example 2>
AGC glass frit “KP312E” (coefficient of thermal expansion: 71 × 10 ⁻⁷ / K, softening point: 344 ° C., SnO content: 52%) manufactured by AGC was used as the inorganic glass except that the firing temperature in the muffle furnace was set to 430 ° C. A joined body was obtained in the same manner as in Example 1.

  About the obtained joined body, the air permeation amount measurement and the durability test were performed. As a result, the air permeability of the joined body before the durability test was 0.1 sccm or less. In addition, the air permeation amount of the joined body after the durability test was 0.1 sccm or less, which was the same before and after the test, indicating that good durability was exhibited.

<Example 3>
Joining was performed in the same manner as in Example 1, except that AGC Glass Frit “FP-67” (thermal expansion coefficient 79 × 10 ⁻⁷ / K, softening point 357 ° C., SnO content 50%) was used as the inorganic glass. I got a body.

  About the obtained joined body, the amount of air permeation was measured. As a result, the air permeation amount of the joined body was 0.1 sccm or less.

<Example 4>
AGC glass frit “BNL115BB” (thermal expansion coefficient 74 × 10 ⁻⁷ / K, softening point 397 ° C., B ₂ O ₃ content 5.0%) manufactured by AGC was used as the inorganic glass, and the firing temperature in the muffle furnace was 500. A joined body was obtained in the same manner as in Example 1 except that the temperature was changed to ° C.

  About the obtained joined body, the air permeation amount measurement and the durability test were performed. As a result, the air permeation amount of the joined body before the durability test was 0.4 sccm. Further, the air permeability of the joined body after the durability test was 0.4 sccm, and there was no change in the airtightness.

<Example 5>
A sealing treatment was performed on the joined body of Example 4. Specifically, a methyl silicate oligomer “MKC silicate (registered trademark) MS-56” manufactured by Mitsubishi Chemical Co., Ltd. is applied to the joint between the cap and the composite of the MFI zeolite and the alumina porous support while reducing the pressure inside. did. After leaving it at room temperature for 1 hour, it was heated at 250 ° C. for 30 minutes to complete the sealing treatment.

  About the obtained joined body, the air permeation amount measurement and the durability test were performed. As a result, the air permeation amount of the joined body before the durability test was 0.1 sccm or less, and it was found that the hermeticity was improved by the sealing treatment. In addition, the air permeation amount of the joined body after the durability test was 0.1 sccm or less, which was the same before and after the test, indicating that good durability was exhibited.

<Example 6>
A glass frit “BF-0606” manufactured by NEC Corporation (coefficient of thermal expansion: 72 × 10 ⁻⁷ / K, softening point: 450 ° C., B ₂ O ₃ content: 6.4%) was used as an inorganic glass in a muffle furnace. A joined body was obtained in the same manner as in Example 1 except that the firing temperature was 485 ° C.

  About the obtained joined body, the air permeation amount measurement and the durability test were performed. As a result, the air permeation amount of the joined body before the durability test was 0.2 sccm. The air permeability of the joined body after the durability test was 0.2 sccm, and there was no change in the airtightness.

<Example 7>
A glass frit “BF-0901” manufactured by NEC Corporation (thermal expansion coefficient: 48 × 10 ⁻⁷ / K, softening point: 528 ° C., B ₂ O ₃ content: 9.7%) was used as an inorganic glass in a muffle furnace. A joined body was obtained in the same manner as in Example 1 except that the firing temperature was 560 ° C.

  About the obtained joined body, the air permeation amount measurement and the durability test were performed. As a result, the air permeability of the joined body before the durability test was 0.1 sccm or less. In addition, the air permeation amount of the joined body after the durability test was 0.1 sccm or less, which was the same before and after the test, indicating that good durability was exhibited.

<Example 8>
AGC glass frit “ASF-1094” (thermal expansion coefficient 79 × 10 ⁻⁷ / K, softening point 533 ° C., B ₂ O ₃ content 15%) manufactured by AGC was used as the inorganic glass, and the firing temperature in the muffle furnace was 550. A joined body was obtained in the same manner as in Example 1 except that the temperature was changed to ° C.

  About the obtained joined body, the air permeation amount measurement and the durability test were performed. As a result, the air permeation amount of the joined body before the durability test was 0.3 sccm. The air permeability of the joined body after the durability test was 0.3 sccm, and there was no change in airtightness.

<Example 9>
The glass frit “ASF-1098” manufactured by AGC (thermal expansion coefficient: 54 × 10 ⁻⁷ / K, softening point: 515 ° C., B ₂ O ₃ content: 16%) was used as the inorganic glass, and the firing temperature in the muffle furnace was set to 560. A joined body was obtained in the same manner as in Example 1 except that the temperature was changed to ° C.

  About the obtained joined body, the amount of air permeation was measured. As a result, the air permeation amount of the joined body was 0.7 sccm or less.

<Example 10>
AGC glass frit “ASF-1109” (coefficient of thermal expansion 65 × 10 ⁻⁷ / K, softening point 545 ° C., B ₂ O ₃ content 19%) manufactured by AGC was used as the inorganic glass, and the firing temperature in the muffle furnace was 560. A joined body was obtained in the same manner as in Example 1 except that the temperature was changed to ° C.

  About the obtained joined body, the amount of air permeation was measured. As a result, the air permeation amount of the joined body was 1.2 sccm or less.

<Comparative Example 1>
AGC glass frit “SK-231-300” (thermal expansion coefficient: 84 × 10 ⁻⁷ / K, softening point: 559 ° C., B ₂ O ₃ content: 13%) was used as the inorganic glass, and the firing temperature in a muffle furnace was used. Was set to 580 ° C., and a joined body was obtained in the same manner as in Example 1.

  About the obtained joined body, the amount of air permeation was measured. As a result, the air permeation amount of the joined body was 5.5 sccm or less.

<Comparative Example 2>
AGC company glass frit “KF9173” (thermal expansion coefficient: 98 × 10 ⁻⁷ / K, softening point: 462 ° C., B ₂ O ₃ content: 11%) was used as the inorganic glass, and the firing temperature in the muffle furnace was 520 ° C. A joined body was obtained in the same manner as in Example 1 except that the procedure was repeated.

  About the obtained joined body, the air permeation amount measurement and the durability test were performed. As a result, the air permeation amount of the joined body before the durability test was 7.3 sccm. Further, the air permeability of the joined body after the durability test was 20 sccm or more (measurement range exceeded), and the airtightness was deteriorated.

REFERENCE SIGNS LIST 1 composite of zeolite and inorganic porous support 2 flange made of dense member 3 dense member 4 inorganic glass

Claims (9)

A bonded body in which a composite of zeolite and an inorganic porous support and a dense member are bonded via an inorganic glass, wherein the dense member is a metal member, and the inorganic glass has a coefficient of thermal expansion of 30 × 10 ^A joined body having a temperature of ⁻⁷ / K or more and 90 × 10 ⁻⁷ / K or less and a softening point of 550 ° C. or less.   The joined body according to claim 1, wherein a joint between the complex and the dense member is covered with a sealing film.   The joined body according to claim 2, wherein the sealing film is a silica film. Wherein the inorganic glass is contained SnO and / or _B 2 _{O 3,} assembly according to any one of claims 1 to 3. The joined body according to any one of claims 1 to 4, wherein the dense member has a coefficient of thermal expansion of 30 x ^10-7 / K or more and 200 x ^10-7 / K or less.   A method of using the joined body, wherein the joined body according to any one of claims 1 to 5 is used under a high temperature condition of 100 ° C to 500 ° C and / or a high pressure condition of 0.5 to 10 MPa.   A separation membrane module comprising the joined body according to claim 1.   A reactor comprising the separation membrane module according to claim 7. A method of joining a composite of zeolite and an inorganic porous support, using an inorganic glass, and a dense member, wherein the dense member is a metal member, and the coefficient of thermal expansion of the inorganic glass is 30 × A bonding method, wherein the bonding point is 10 ⁻⁷ / K or more and 90 × 10 ⁻⁷ / K or less and the softening point is 550 ° C. or less.