JP2020023433A - Conjugate, and separation membrane module having the same - Google Patents

Abstract

To provide a conjugate suppressing use of lead, having high airtightness, and further excellent in durability under a condition of high temperature and high pressure.SOLUTION: A conjugate is obtained by joining a complex of zeolite and an inorganic porous support with a dense member with lead-free inorganic glass. In the conjugate, a thermal expansion coefficient of the lead-free inorganic glass is 30×10/K or more and 90×10/K or less, and a softening point is 550°C or lower.SELECTED DRAWING: Figure 1

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. Patent Document 1 discloses a joined body in which a gas separation membrane and a metal member are joined with glass having a coefficient of thermal expansion of 50 × 10 ⁻⁷ to 80 × 10 ⁻⁷ / K. Further, Patent Document 2 discloses a composition for sealing a separation membrane composed of alumina and specific glass containing predetermined amounts of B ₂ O ₃ and PbO. Patent Document 3 discloses a structure in which a ceramic member and a metal member are sealed with glass having a coefficient of thermal expansion of 55 × 10 ^{−7 to} 65 × 10 ⁻⁷ / K.

  When zeolite is used as the membrane having gas separation capability, high-temperature treatment is not preferable because of the heat resistance of the zeolite membrane. The high-temperature treatment at 900 ° C. or higher as disclosed in Patent Literatures 1 and 3 may cause structural deterioration such as breakage of the zeolite membrane, and may lower the separation performance. In addition, joining at a high temperature requires time for heating and cooling, leading to a decrease in efficiency and an increase in cost in mass-producing joined articles.

  On the other hand, it has been proposed to use lead glass as a joined body that has sufficient airtightness, is resistant to temperature changes, withstands reaction pressure, and can be used for a long time. For example, as disclosed in Patent Document 2, it is possible to reduce the firing temperature to 600 ° C. or lower by using a glass containing PbO as a main component. However, it is known that lead accumulates in the body and causes chronic poisoning, and its use has environmental problems, which goes against the trend of restricting lead use worldwide.

JP-A-7-163827 JP-A-10-180060 JP 2013-203602 A

  The present invention is to provide a joined body in which a composite of a zeolite and an inorganic porous support and a dense member are joined together, while suppressing the use of lead and giving consideration to the environment and realizing high airtightness. It is another object of the present invention to improve the durability under high-temperature and high-pressure conditions.

  The present inventors have conducted intensive research, and by joining a composite of zeolite and an inorganic porous support and a dense member with a lead-free inorganic glass having a specific thermal expansion coefficient and a softening point, The inventors have found that the above problems can be solved, and have reached the present invention. The present invention includes the following.

<1> A joined body in which a composite of zeolite and an inorganic porous support and a dense member are joined via a lead-free inorganic glass, and the lead-free inorganic glass has a coefficient of thermal expansion of 30 × 10 ^−7. / K and 90 * 10 < ^-7 > / K or less, and the softening point is 550 degreeC 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 lead-free 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 thermal expansion coefficient 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 <6>.
<8> A reactor having the separation membrane module according to <7>.
<9> A joining method using a lead-free inorganic glass to join a composite of zeolite and an inorganic porous support to a dense member, wherein the lead-free inorganic glass has a coefficient of thermal expansion of 30 × 10 ^{− A} bonding method, wherein the bonding temperature is from ⁷ / K to 90 × 10 ⁻⁷ / K and the softening point is 550 ° C. or less.

  According to the present invention, a composite of a zeolite and an inorganic porous support, which is a separation membrane, and a dense member, when producing a bonded body, by using a specific lead-free inorganic glass as a glass-based adhesive Further, it is possible to provide a bonded body that reduces damage to the zeolite during bonding and has 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 a lead-free inorganic glass. FIG. 3 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 a lead-free 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 a lead-free 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, TON, TSC, UFI, VNI, WEI, YUG, and the like. It is preferably one selected from these.

  In addition, the conjugate according to the present invention is a simple molecular sieve, that is, a zeolite selectively adsorbs an object to be separated by a zeolite not for the purpose of permeating molecules as a sieve simply due to a difference in molecular size. More preferably, it can be used for the purpose of permeating the above molecules or separating molecules of the same size. That is, it is more preferable that the target substance is separated by selective adsorption on the surface of zeolite. If the use temperature of such a zeolite is too high, the selective adsorption ability is weakened. For example, under a temperature condition of about 500 ° C. or less, 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 untreated gas does not react, and excellent in mechanical strength, specifically, various types of alumina, silica, In addition to oxide ceramics such as silica-alumina, mullite, cordierite, and zirconia, silicon carbide, carbon, and glass can be used.
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 heat, the denseness can be maintained and the selectivity of the film can be kept high. 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 a member having such a denseness (confidentiality) that a gas used for a reaction or a reacted gas does not leak from the member. The member is not particularly limited as long as it is a member having such denseness, and typically, a metal is used. Examples of the metal mentioned here include a SUS tube made of stainless steel, ceramics such as alumina and zirconia, and an alloy such as Kovar.
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 at most 150 × 10 ⁻⁷ / K, more preferably at most 120 × 10 ⁻⁷ / K, even more preferably at most 85 × 10 ⁻⁷ / K. When the thermal expansion coefficient of the dense member is in the above range, the difference from the thermal expansion coefficient of the lead-free inorganic glass is small, and good sealing properties (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. The measurement of the coefficient of thermal expansion is performed 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.

<Lead-free inorganic glass>
In this embodiment, the lead-free inorganic glass means that the content of lead (Pb) is 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less in terms of PbO. Particularly preferred is 1% by mass or less, most preferably 0% by mass of inorganic glass.

The lead-free 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, Further, 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 lead-free 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 usually 200% or less, preferably Is at most 150%, more preferably at most 120%. Since the thermal expansion coefficient of the lead-free inorganic glass is equal to or less than the upper limit, when the temperature is decreased after joining at a temperature at which the lead-free inorganic glass is melted, tensile stress is not easily generated inside the joined portion, Cracks at the joint are suppressed. On the other hand, when the thermal expansion coefficient 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 use temperature range of the joined body, and the separation target gas is moved from the gap to the purified gas side. Leakage can be suppressed.

The joined body obtained by joining the composite and the dense member with such a lead-free inorganic glass has an air permeation amount of 10 sccm or less in the test method described in the section of the present example. It is more preferably 8 sccm or less, and most preferably 5 sccm or less.
Further, the conjugate was added with 1/16 by volume of methanol and 1/16 of demineralized water with respect to the internal volume in the autoclave, the temperature was raised to 280 ° C. in 1 hour, and this state was maintained for 48 hours. After that, the mixture is naturally cooled, dried at 120 ° C. for 4 hours under normal pressure, 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 conditions in addition to the condition of the coefficient of thermal expansion, when a separation membrane module having a bonded body is installed in a methanol synthesis reactor, even if methanol is produced for a longer period of time, the bonded portion is not damaged. This is more preferable because there is no problem.

  When the separation module having the joined body according to the present embodiment is used industrially, it may be reciprocated between room temperature and the use temperature many times, and may be operated at the use temperature for a long time. is there. Therefore, the joint formed by the lead-free inorganic glass is required to prevent the gas to be separated from leaking even under these high-temperature and high-pressure conditions, and the thermal expansion coefficient of the lead-free inorganic glass is set as described above. Thereby, leakage of the gas to be separated can be suppressed.

  The lead-free 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 lead-free 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 lead-free inorganic glass within the above range, zeolite and the lead-free inorganic glass can be chemically bonded at a relatively low temperature of about 600 ° C. or less, and the fineness of the composite can be reduced. The lead-free inorganic glass enters the pores, 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.

The lead-free inorganic glass is not particularly limited as long as it has the above-mentioned coefficient of thermal expansion and softening point. Components contained in the lead-free inorganic glass include, for example, 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 , SnO and the like. Among these, the lead-free inorganic glass preferably contains B ₂ O ₃ and / or SnO from the viewpoint of improving sealing properties. Specific examples of the lead-free inorganic glass containing B ₂ O ₃ and / or SnO include SnO—P ₂ O ₅ glass, Bi ₂ O ₃ —ZnO glass, and Bi ₂ O ₃ —B ₂ O ₃ glass. _{glass, Bi 2 O 3 -B 2 O} 3 -SiO 2 based _{glass, Bi 2 O 3 -ZnO-B} 2 O 3 based glass, and the like. Commercially available glass frit of such a lead-free inorganic glass include “FP-74”, “KP312E”, “FP-67”, “BNL115BB”, “ASF-1094”, “ASF-1098”, “ASF” -1109 "(all manufactured by AGC);" BF-0606 "and" BF-0901 "(all manufactured by NEC Corporation);

When the lead-free 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 20% by mass or more, more preferably 30% by mass or more.
By setting the SnO content in this range, the fluidity of the glass is sufficiently maintained, and sufficient sealing performance 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 presumed that this leads to an improvement in sealing performance.

On the other hand, when the lead-free 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. It is. 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 sealing property (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.

The form of the lead-free inorganic glass is not particularly limited, and powdered glass frit, a tablet formed by molding a glass frit by tableting, a tablet obtained by sintering a glass frit, and a glass frit formed of an organic material are used. A glass paste or the like uniformly dispersed in a solvent or 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.

<Joint of 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, can join the composite and the cap with a lead-free inorganic glass. Any method may be used as long as it is a method, for example, a lead-free inorganic glass is filled in a concave portion of a dense member, a composite having a zeolite membrane on the surface is placed thereon, and then a weight is placed on the upper portion of the composite. For example, a method of joining by firing under a load.

  It is essential that the firing temperature at the time of joining the composite and the dense member with the lead-free inorganic glass be equal to or higher than the softening point of the lead-free inorganic glass used. Therefore, the sintering temperature is usually at least the softening point plus 10 ° C, preferably at least the softening point of the lead-free inorganic glass 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 a lead-free 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 a lead-free 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 becomes a dense 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 lead-free inorganic glass 4. Since the lead-free 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.
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 a lead-free inorganic glass 4. The composite 1 of zeolite and the inorganic porous support is joined to the pipe 3 via the lead-free inorganic glass 4. The pipe 3 is joined so as to cover the composite 1 of zeolite and the inorganic porous support.
Incidentally, the "bonded body" of the present invention is a composite of a zeolite and an inorganic porous support, and a dense member is bonded, the performance of the composite is reduced, when replacing this Although it is a removable part, if it does not have such a removing mechanism, for example, if it is incorporated in a reactor such as a methanol synthesis reactor, it shall include the dense member inside the reactor.

<Sealing coating>
In this embodiment, it is preferable that the joint between the composite and the dense member is covered with a sealing film. The joint portion may have micropores such as microcracks and pinholes formed on the surface of the joint portion due to firing for hardening the lead-free inorganic glass used for joining. Therefore, it is preferable from the viewpoint of improving the sealing property (airtightness) to perform a sealing treatment on the joint portion and close these micropores. 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 the like. 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 a lead-free inorganic glass and gas barrier properties. In addition, a silicone resin is preferably used in that a dense film is formed. The amount of the sealing agent to be applied may be appropriately determined according to the desired 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 handleability of the sealing agent, particularly prevention of dripping. s, 25 ° C) or higher. Further, 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. Within this range, the sealing property (airtightness) is improved, and the handling property 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 sealing property (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 silicate oligomers 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. 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, the original chemical equilibrium can always be moved in a direction advantageous for production in a production method utilizing a reaction in which a reverse reaction can occur, thereby improving the yield. It can be used for a long time with little risk of breakage.

<Use conditions>
When using the joined body of this embodiment in an organic chemical reaction process, the temperature is usually 100 to 450 ° C, and 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. In addition, various measurements and evaluations in the examples were performed as follows.

<Coefficient of thermal expansion of lead-free inorganic glass and dense members>
The coefficient of thermal expansion (linear expansion coefficient) of the glass frit and the dense member of the lead-free inorganic glass 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 the sample. Is measured with a differential thermal dilatometer (TMA8310, manufactured by Rigaku Corporation) to calculate the average coefficient of linear expansion. In this example, catalog values were used.

<Softening point of lead-free 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 placed in 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. Thereafter, the container was sealed under atmospheric pressure and set in an electric furnace. The electric furnace was heated to 280 ° C. 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” (thermal) with lead-free inorganic glass in the recess of a Kovar cap (coefficient of thermal expansion 52 × 10 ⁻⁷ / K, outer diameter 14.0 mm, inner diameter 12.2 mm, height 4 mm) 0.3 g of an expansion coefficient of 63 × 10 ⁻⁷ / K, a softening point of 355 ° C., and a SnO content of 42%) were charged, 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. Further, it was found that the air permeation amount of the joined body after the durability test was 0.1 sccm or less, which was not changed before and after the test, and showed good durability.

<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 lead-free inorganic glass, and the firing temperature in the muffle furnace was 430 ° C. Except for the above, 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. Further, it was found that the air permeation amount of the joined body after the durability test was 0.1 sccm or less, which was not changed before and after the test, and showed good durability.

<Example 3>
A method similar to that of 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 a lead-free inorganic glass. To obtain a joined 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 as a lead-free inorganic glass, and firing temperature in a muffle furnace Was set to 500 ° C., and 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 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 sealability.

<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. When the air permeation amount was measured, it was 0.1 sccm or less, and the sealing property was improved by the sealing treatment.

  About the obtained joined body, the air permeation amount measurement and the durability test were performed. As a result, it was found that the air permeation amount of the joined body before the durability test was 0.1 sccm or less, and the sealing property was improved by the sealing treatment. Further, it was found that the air permeation amount of the joined body after the durability test was 0.1 sccm or less, which was not changed before and after the test, and showed good durability.

<Example 6>
A muffle furnace using 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%) as a lead-free inorganic glass. A joined body was obtained in the same manner as in Example 1 except that the firing temperature at 485 ° C. was set to 485 ° C. The amount of air permeation measured in the same manner as in Example 1 was 0.2 sccm.

  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. Further, the air permeability of the joined body after the durability test was 0.2 sccm, and there was no change in the sealability.

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

  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-made glass frit “ASF-1094” (thermal expansion coefficient 79 × 10 ⁻⁷ / K, softening point 533 ° C., B ₂ O ₃ content 15%) as a lead-free inorganic glass, and firing temperature in a muffle furnace Was set to 550 ° C., and a joined body was obtained in the same manner as in Example 1. The amount of air permeation measured in the same manner as in Example 1 was 0.3 sccm.

  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. Further, the air permeability of the joined body after the durability test was 0.3 sccm, and there was no change in the sealability.

<Example 9>
AGC-made glass frit "ASF-1098" (thermal expansion coefficient: 54 × 10 ⁻⁷ / K, softening point: 515 ° C., B ₂ O ₃ content: 16%) as a lead-free inorganic glass, and firing temperature in a muffle furnace Was set to 560 ° 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 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 as a lead-free inorganic glass, and firing temperature in a muffle furnace Was set to 560 ° 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 1.2 sccm or less.

<Comparative Example 1>
AGC-made glass frit “SK-231-300” (coefficient of thermal expansion: 84 × 10 ⁻⁷ / K, softening point: 559 ° C., B ₂ O ₃ content: 13%) was used as a lead-free 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 580 ° C. The amount of air permeation measured in the same manner as in Example 1 was 5.5 sccm.

  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 glass frit “KF9173” (thermal expansion coefficient 98 × 10 ⁻⁷ / K, softening point 462 ° C., B ₂ O ₃ content 11%) manufactured by AGC is used as a lead-free inorganic glass, and the firing temperature in a muffle furnace is 520. A joined body was obtained in the same manner as in Example 1 except that the temperature was changed to ° C. The amount of air permeation measured in the same manner as in Example 1 was 7.3 sccm.

  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 permeation amount of the joined body after the durability test was 20 sccm or more (measurement range exceeded), and the sealability was deteriorated.

REFERENCE SIGNS LIST 1 composite of zeolite and inorganic porous support 2 flange made of dense member 3 pipe made of dense member 4 lead-free 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 a lead-free inorganic glass, wherein the lead-free inorganic glass has a coefficient of thermal expansion of 30 × 10 ⁻⁷ / K or more. A joined body having a ^{hardness of} 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. Lead-free mineral 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 for joining a composite of zeolite and an inorganic porous support and a dense member using a lead-free inorganic glass, wherein the lead-free inorganic glass has a coefficient of thermal expansion of 30 × 10 ⁻⁷ / K. The bonding method, wherein the bonding temperature is 90 × 10 ⁻⁷ / K or less and the softening point is 550 ° C. or less.