JP7011251B2 - Acid-resistant and alkali-resistant sealed glass and zeolite separation membrane using it - Google Patents
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Description
本発明は、例えば、化学プラントに適応されるゼオライト分離膜等の耐アルカリ性や耐酸性等の耐化学薬品性が要求される箇所に使用され、且つ、セラミック部材同士を接合するために使用される封着ガラス及びそれを用いて製作されるゼオライト分離膜に関する。 The present invention is used, for example, in places where chemical resistance such as alkali resistance and acid resistance is required, such as zeolite separation membranes suitable for chemical plants, and is used for joining ceramic members to each other. The present invention relates to a sealing glass and a zeolite separation membrane produced by using the sealing glass.
化学プラントにおいて、種々の化学物質を取り扱う関係から耐アルカリ性や耐酸性の耐化学薬品性の高いセラミック部材等が多用されている。これらのセラミック部材を組み合わせて構造体を製作する接合技術としてガラス接着法が一般に用いられている。 In chemical plants, ceramic members having high alkali resistance and acid resistance and high chemical resistance are often used because they handle various chemical substances. The glass bonding method is generally used as a bonding technique for manufacturing a structure by combining these ceramic members.
例えば、ゼオライトを分離膜として利用する場合、ゼオライト層自体には十分な機械的強度がないため、支持体となるセラミック多孔質管の表面にゼオライトの結晶を薄層状に析出させ、ゼオライト層を支持させた状態とする。このようなゼオライト層を形成する方法としては、セラミック多孔質管の表面にゼオライトの種結晶を付着させ、これをシリカ源とアルミナ源からなる原料溶液を混合した反応液に浸漬し、反応液を攪拌しながら水熱合成する水熱合成法が知られている。 For example, when zeolite is used as a separation membrane, the zeolite layer itself does not have sufficient mechanical strength, so zeolite crystals are deposited in a thin layer on the surface of the ceramic porous tube to be the support to support the zeolite layer. It is in the state of being let. As a method for forming such a zeolite layer, a zeolite seed crystal is adhered to the surface of a ceramic porous tube, and this is immersed in a reaction solution in which a raw material solution consisting of a silica source and an alumina source is mixed, and the reaction solution is prepared. A hydrothermal synthesis method is known in which hydrothermal synthesis is performed while stirring.
支持体となるセラミック多孔質管には、ゼオライト層を形成する前に、管端の封止用や膜モジュールへの固定用に、支持体よりも緻密なセラミックからなる接合部材を取り付ける必要があり、その方法の一つとしてガラス接着法が用いられている。 Before forming the zeolite layer, it is necessary to attach a joining member made of ceramic, which is denser than the support, to the ceramic porous tube to be the support for sealing the tube end and fixing to the membrane module. , The glass bonding method is used as one of the methods.
特許文献1には、アルミナを主成分とする多孔質管と封止栓等の接合部材とを接合するための接合剤が記載されており、本接合剤は必須成分としてSiO2:17~48wt%、Al2O3:2~8wt%、BaO:24~60wt%、ZnO:0.5~5wt%を含み、かつLa2O3、CaOおよびSrOのうち少なくとも1つを含み、必須成分が全体重量の80~84.5wt%であり、La2O3、CaOおよびSrOのうちの少なくとも1つが全体重量の11.7~15.8wt%の組成を有するものである。 Patent Document 1 describes a bonding agent for bonding a porous tube containing alumina as a main component and a bonding member such as a sealing stopper, and this bonding agent contains SiO 2 : 17 to 48 wt as an essential component. %, Al 2 O 3 : 2 to 8 wt%, BaO: 24 to 60 wt%, ZnO: 0.5 to 5 wt%, and at least one of La 2 O 3 , CaO and SrO, and the essential components are It is 80 to 84.5 wt% of the total weight, and at least one of La 2O 3 , CaO and SrO has a composition of 11.7 to 15.8 wt% of the total weight.
非特許文献1には、耐アルカリ性を有する液面計用ガラスとして、SiO2、Al2O3、Y2O3、ZrO2、TiO2、La2O3、MgO、CaO、BaO、ZnO、B2O3、F、Sb2O3、およびAs2O3の配合比を変えたガラスの特性が記載されている。 Non-Patent Document 1 states that the glass for a liquid level gauge having alkali resistance includes SiO 2 , Al 2 O 3 , Y 2 O 3 , ZrO 2 , TiO 2 , La 2 O 3 , MgO, CaO, BaO, ZnO, and the like. The characteristics of the glass with different compounding ratios of B 2 O 3 , F, Sb 2 O 3 , and As 2 O 3 are described.
近年、ゼオライト分離膜等が化学プラントにおいて多用され、種々の被分離物質に対応することができるようにするために、被分離物質が強アルカリ性や強酸性を示す場合でも利用可能なゼオライト分離膜等が要望されている。 In recent years, zeolite separation membranes and the like have been widely used in chemical plants, and in order to be able to handle various substances to be separated, zeolite separation membranes and the like that can be used even when the substances to be separated show strong alkalinity or strong acidity. Is requested.
本発明は、化学プラント等で用いられるセラミック部材等の接合に用いられ、耐アルカリ性と耐酸性が要求される封着ガラスおよびそれを用いて製作されるゼオライト分離膜を提供することを課題とする。 An object of the present invention is to provide a sealed glass used for joining ceramic members and the like used in a chemical plant and the like, which is required to have alkali resistance and acid resistance, and a zeolite separation membrane manufactured by using the sealed glass. ..
上記課題を解決すべく、本発明1は、 セラミックの封着ガラスであって、主成分であるSiO2、CaOおよびAl2O3の含有モル比が、3元系状態図における(I)(SiO2:CaO:Al2O3)=(57.0:40.0:3.0)、(II)(SiO2:CaO:Al2O3)=(53.5:40.0:6.5)、(III)(SiO2:CaO:Al2O3)=(60.5:33.0:6.5)、(IV)(SiO2:CaO:Al2O3)=(64.0:33.0:3.0)の4点に囲まれている範囲であることを特徴としている。 In order to solve the above problems, the present invention 1 is a ceramic sealed glass in which the molar ratios of the main components SiO 2 , CaO and Al 2 O 3 are (I) (I) in the ternary state diagram. SiO 2 : CaO: Al 2 O 3 ) = (57.0: 40.0: 3.0), (II) (SiO 2 : CaO: Al 2 O 3 ) = (53.5: 40.0: 6) .5), (III) (SiO 2 : CaO: Al 2 O 3 ) = (60.5: 33.0: 6.5), (IV) (SiO 2 : CaO: Al 2 O 3 ) = (64) It is characterized in that it is a range surrounded by four points (0.0: 33.0: 3.0).
主成分は、SiO2、CaOおよびAl2O3であり、これらの3成分を主成分とし、これらの主成分の含有モル比を上記(I)~(IV)に囲まれた範囲内とすることで、耐アルカリ性が高く、かつ耐酸性も高い封着ガラスを実現することができる。 The main components are SiO 2 , CaO and Al 2 O 3 , and these three components are the main components, and the molar ratio of these main components is within the range surrounded by the above (I) to (IV). As a result, it is possible to realize a sealed glass having high alkali resistance and high acid resistance.
本発明2は、本発明1に記載の封着ガラスであって、当該封着ガラスの封着温度が800℃~1000℃であることを特徴としている。
The
封着ガラスの封着温度は、封着ガラスによって接合されたセラミック部材等が化学プラント等で使用される温度よりも十分に高く、逆に封着温度が高すぎると製作が困難となるため、高くなりすぎないようすることが重要である。 The sealing temperature of the sealing glass is sufficiently higher than the temperature at which the ceramic members joined by the sealing glass are used in chemical plants, etc. On the contrary, if the sealing temperature is too high, it becomes difficult to manufacture. It is important not to get too high.
封着させるためには封着ガラスの軟化温度より高い800℃以上の温度が必要であるが、特にゼオライト分離膜では、封着温度が1000℃を超えると、封着の際の熱によりセラミック多孔質管の細孔径に影響を及ぼす恐れがある。封着温度が800℃~1000℃であると、ゼオライト分離膜の使用温度(500℃以下)に比べて十分に高く、一般のガラスの封着温度に比べて低く好ましい。 In order to seal, a temperature of 800 ° C or higher, which is higher than the softening temperature of the sealed glass, is required. Especially for zeolite separation membranes, when the sealing temperature exceeds 1000 ° C, the ceramic is porous due to the heat of sealing. It may affect the pore size of the pouch. When the sealing temperature is 800 ° C. to 1000 ° C., it is sufficiently higher than the operating temperature (500 ° C. or lower) of the zeolite separation membrane, and lower than the sealing temperature of general glass, which is preferable.
本発明3は、封着ガラスの線膨張係数が4~9×10-6(/K)であることを特徴とする本発明1または2のいずれかに記載の封着ガラスである。
The present invention 3 is the sealing glass according to any one of the
セラミック材料の線膨張係数は、例えばジルコニアセラミックでは10×10-6/Kであり、アルミナセラミックでは7.2×10-6/Kであり、炭化ケイ素セラミックでは4.4×10-6/Kである。したがって、封着ガラスの線膨張係数が4~9×10-6(/K)であると、セラミック材料の線膨張係数に近く、温度変化によってセラミック部材に挟まれた封着ガラスに過大な応力が加わらず、クラック等が発生せず耐久性が向上する。 The linear expansion coefficient of the ceramic material is, for example, 10 × 10-6 / K for zirconia ceramics, 7.2 × 10-6 / K for alumina ceramics, and 4.4 × 10-6 / K for silicon carbide ceramics. Is. Therefore, when the linear expansion coefficient of the sealing glass is 4 to 9 × 10 -6 (/ K), it is close to the linear expansion coefficient of the ceramic material, and excessive stress is applied to the sealing glass sandwiched between the ceramic members due to the temperature change. Is not added, cracks and the like do not occur, and durability is improved.
本発明4は、セラミック多孔質管の表面にゼオライト層が形成されたゼオライト分離膜であって、当該ゼオライト分離膜は、支持体となるセラミック多孔質管の管端を封止または膜モジュールに固定するためのセラミック接合部材を有し、セラミック多孔質管と前記セラミック接合部材は、本発明1~3のいずれか1つに記載の封着ガラスによって接合されていることを特徴としている。 The present invention 4 is a zeolite separation membrane in which a zeolite layer is formed on the surface of a ceramic porous tube, and the zeolite separation membrane seals the tube end of the ceramic porous tube as a support or fixes it to a membrane module. The ceramic porous tube and the ceramic joining member are joined by the sealing glass according to any one of the present inventions 1 to 3.
本発明4によるゼオライト分離膜は、接合剤として用いられる封着ガラスの耐アルカリ性および耐酸性が高いため耐久性が向上する。 The zeolite separation membrane according to the present invention 4 has high alkali resistance and acid resistance of the sealed glass used as a bonding agent, so that the durability is improved.
セラミック多孔質体の表面にゼオライト層を形成する方法は、特許文献1に記載してある方法と同じである。 The method for forming the zeolite layer on the surface of the ceramic porous body is the same as the method described in Patent Document 1.
本発明は、化学プラント等で用いられるセラミック部材等の接合に用いられ、耐アルカリ性と耐酸性が要求される封着ガラスおよびそれを用いて製作されるゼオライト分離膜を提供する。 The present invention provides a sealed glass used for joining ceramic members and the like used in chemical plants and the like, which is required to have alkali resistance and acid resistance, and a zeolite separation membrane manufactured by using the sealed glass.
つぎに、本発明の実施の形態を説明するが、本発明はこれらに限定されるものではない。 Next, embodiments of the present invention will be described, but the present invention is not limited thereto.
本発明の封着ガラスの組成決定の前に、特許文献1および非特許文献1に開示されたガラスの耐アルカリ性と耐酸性の試験を行った。 Prior to determining the composition of the sealed glass of the present invention, the alkali resistance and acid resistance of the glass disclosed in Patent Document 1 and Non-Patent Document 1 were tested.
耐アルカリ性試験および耐酸性試験に供するガラスの試験サンプルは、各組成の原料粉末を秤量・混合し、Pt坩堝にて1600℃で2Hr程度溶融させて製作した。 The glass test samples to be subjected to the alkali resistance test and the acid resistance test were produced by weighing and mixing the raw material powders of each composition and melting them in a Pt crucible at 1600 ° C. for about 2 hours.
耐アルカリ試験では、9×9×2mmの板状に成形し、その後表面に傷が見られなくなるまで研磨したサンプルを耐圧硝子工業(株)製のテフロン(登録商標)内筒密閉容器(型番:TAF-SR-50)にテフロン糸で括って吊るし、そこへ1.3mol/LのNaOH溶液(30ml)を封入し、180℃で72時間の浸漬曝露試験を行い、曝露前後の重量測定により評価した。 In the alkali resistance test, a sample formed into a 9 x 9 x 2 mm plate and then polished until no scratches are seen on the surface is used as a Teflon (registered trademark) inner cylinder closed container manufactured by Pressure-Resistant Glass Industry Co., Ltd. (model number: TAF-SR-50) is wrapped with Teflon thread and hung, filled with 1.3 mol / L NaOH solution (30 ml), subjected to immersion exposure test at 180 ° C for 72 hours, and evaluated by weight measurement before and after exposure. did.
図2の10がテフロン内筒密閉容器であり、11がテフロン糸であり、12がテフロン内筒であり、13が浸漬液であり、14が試験に供したテストサンプルである。 10 in FIG. 2 is a Teflon inner cylinder closed container, 11 is a Teflon thread, 12 is a Teflon inner cylinder, 13 is an immersion liquid, and 14 is a test sample used for the test.
耐酸性試験では、耐アルカリ性試験と同様にサンプルをセットし、pHが3となるように調整した酢酸水溶液を封入し、180℃で72時間の浸漬曝露試験を行い、曝露前後の重量測定により評価した。 In the acid resistance test, a sample is set in the same manner as the alkali resistance test, an acetic acid aqueous solution adjusted to have a pH of 3 is enclosed, an immersion exposure test is conducted at 180 ° C. for 72 hours, and evaluation is performed by weight measurement before and after exposure. did.
下記表1は、特許文献1および非特許文献1に開示されたガラスの成分および耐アルカリ性と耐酸性試験の試験結果を示す。成分はモル比(%)で、耐アルカリ性と耐酸性試験の試験結果は、試験前の試験サンプルの重量に対する試験後の減量重量の比(%)で示す。 Table 1 below shows the components of the glass disclosed in Patent Document 1 and Non-Patent Document 1 and the test results of the alkali resistance and acid resistance test. The component is a molar ratio (%), and the test results of the alkali resistance and acid resistance test are shown by the ratio (%) of the weight loss after the test to the weight of the test sample before the test.
これに対して、非特許文献1に開示のガラスの耐アルカリ性試験の試験結果は1.6%と比較的良好であるが、耐酸性試験の試験結果は6.8%と悪い。 On the other hand, the test result of the alkali resistance test of glass disclosed in Non-Patent Document 1 is relatively good at 1.6%, but the test result of the acid resistance test is bad at 6.8%.
本発明の目的とする耐アルカリ性が非常に高く、かつ耐酸性も非常に高い封着ガラスの組成比を決定するために以下の試験を行った。 The following tests were conducted to determine the composition ratio of the sealed glass, which is the object of the present invention and has very high alkali resistance and very high acid resistance.
アルカリ金属酸化物を組成に加えると耐アルカリ性が悪くなるという経験から、ガラス成分としてSiO2にアルカリ土類金属の酸化物を加え、封着温度を下げるためのAl2O3の3元素を基本主成分として封着ガラスを作製することとした。 Based on the experience that alkali resistance deteriorates when an alkali metal oxide is added to the composition, an alkali earth metal oxide is added to SiO 2 as a glass component, and the three elements of Al 2 O 3 for lowering the sealing temperature are basic. We decided to make sealed glass as the main component.
アルカリ土類金属をBaとし、その酸化物のBaOを用いたが、耐アルカリ性試験が18.7%と非常に悪かったため、Ca酸化物のCaOを主成分に加えることとした。 The alkaline earth metal was Ba, and the oxide BaO was used, but the alkali resistance test was very poor at 18.7%, so it was decided to add CaO, which is a Ca oxide, as the main component.
SiO2、CaOおよびAl2O3の3元素を下記表2の配合モル比で配合した試験サンプルa~rを製作し、耐アルカリ性試験および耐酸性試験を行った。 Test samples a to r in which the three elements of SiO 2 , CaO and Al 2 O 3 were blended at the blending molar ratios shown in Table 2 below were prepared, and alkali resistance test and acid resistance test were performed.
図3に、耐アルカリ性試験の試験結果を3元系状態図内に示している。矢印の起点が試験サンプルa~rの3元系状態図における位置を示し、矢印の長さが耐アルカリ性試験の結果を示している。矢印の長さが長いほど耐アルカリ性が悪く、矢印の長さが短いほど耐アルカリ性が良いことを示している。矢印の線幅が太いものは、耐アルカリ性試験が1%以下のものを示し、矢印の線幅が細いものは耐アルカリ性試験が1%を超えるものを示している。 FIG. 3 shows the test results of the alkali resistance test in the ternary phase diagram. The starting point of the arrow indicates the position of the test samples a to r in the ternary phase diagram, and the length of the arrow indicates the result of the alkali resistance test. The longer the length of the arrow, the worse the alkali resistance, and the shorter the length of the arrow, the better the alkali resistance. The one with a wide arrow line width indicates that the alkali resistance test is 1% or less, and the one with a narrow arrow line width indicates that the alkali resistance test exceeds 1%.
この図3を見ると、図中のY1とY2を結ぶ線の左側に耐アルカリ性試験が1%以下のものが集中していることがわかる。なお、サンプルiおよびjは試験サンプルがガラス化しなかったため試験を行わなかった。 Looking at FIG. 3, it can be seen that those having an alkali resistance test of 1% or less are concentrated on the left side of the line connecting Y1 and Y2 in the figure. The samples i and j were not tested because the test samples were not vitrified.
図4に、耐酸性試験の試験結果を3元系状態図内に示している。図3と同じく、矢印の起点が試験サンプルa~rの3元系状態図における位置を示し、矢印の長さが耐酸性試験の結果を示している。矢印の長さが長いほど耐酸性が悪く、矢印の長さが短いほど耐酸性が良いことを示している。矢印の線幅が太いものは、耐酸性試験が1%以下を示し、矢印の線幅が細いものは耐酸性試験が1%を超えるものを示している。 FIG. 4 shows the test results of the acid resistance test in the ternary phase diagram. Similar to FIG. 3, the starting point of the arrow indicates the position of the test samples a to r in the ternary phase diagram, and the length of the arrow indicates the result of the acid resistance test. The longer the arrow length, the worse the acid resistance, and the shorter the arrow length, the better the acid resistance. Those with a wide arrow line indicate that the acid resistance test is 1% or less, and those with a narrow arrow line width indicate that the acid resistance test exceeds 1%.
この図4を見ると、図中のX1とX2を結ぶ線の上側に耐酸性試験が1%以下のものが集中していることがわかる。 Looking at FIG. 4, it can be seen that those having an acid resistance test of 1% or less are concentrated on the upper side of the line connecting X1 and X2 in the figure.
図3および図4に示された試験結果から、耐アルカリ性が1%以下で、かつ耐酸性試験結果が1%以下であるものは、図5中のY1とY2を結ぶ線の左側で、かつX1とX2を結ぶ線の上側にある領域にある試験サンプルmとrのみで、試験サンプルmとrが含まれる近傍の領域を3元系状態図におけるポイント(点)I、II、III、IVで取り囲んでいる。この領域内部の組成のガラスは、耐アルカリ性と耐酸性が良いことがわかる。 From the test results shown in FIGS. 3 and 4, those having an alkali resistance of 1% or less and an acid resistance test result of 1% or less are on the left side of the line connecting Y1 and Y2 in FIG. Only the test samples m and r in the region above the line connecting X1 and X2, and the region in the vicinity where the test samples m and r are included are the points (points) I, II, III, IV in the ternary phase diagram. Surrounded by. It can be seen that the glass having a composition inside this region has good alkali resistance and acid resistance.
点I、II、III、IVそれぞれのSiO2、CaOおよびAl2O3の含有モル比は以下に示す通りである。 The molar ratios of SiO 2 , CaO and Al 2 O 3 at points I, II, III and IV respectively are as shown below.
(I) (SiO2:CaO:Al2O3)=(57.0:40.0:3.0)
(II)(SiO2:CaO:Al2O3)=(53.5:40.0:6.5)
(III)(SiO2:CaO:Al2O3)=(60.5:33.0:6.5)
(IV)(SiO2:CaO:Al2O3)=(64.0:33.0:3.0)
主要成分が、SiO2、CaO及びAl2O3の3成分であって、3元系状態図における上記点(I)~(IV)で囲まれる領域をモル組成比とする封着ガラスは、耐アルカリ性及び耐酸性の試験結果が共に1%以下を示す。これは、耐アルカリ性に優れる非特許文献1に記載のガラスに比べてガラスの溶出量は36%以上減少し、耐酸性に優れる特許文献1に記載のガラスに比べてもガラスの溶出量は50%以上減少している。
(I) (SiO 2 : CaO: Al 2O 3 ) = (57.0: 40.0: 3.0)
(II) (SiO 2 : CaO: Al 2O 3 ) = (53.5: 40.0: 6.5)
(III) (SiO 2 : CaO: Al 2O 3 ) = (60.5: 33.0: 6.5)
(IV) (SiO 2 : CaO: Al 2O 3 ) = (64.0: 33.0: 3.0)
The sealing glass has three main components, SiO 2 , CaO and Al 2 O 3 , and the region surrounded by the above points (I) to (IV) in the ternary phase diagram is the molar composition ratio. Both alkali resistance and acid resistance test results show 1% or less. This is because the elution amount of the glass is reduced by 36% or more as compared with the glass described in Non-Patent Document 1 which is excellent in alkali resistance, and the elution amount of the glass is 50 as compared with the glass described in Patent Document 1 which is excellent in acid resistance. It has decreased by more than%.
また、図4によれば、サンプルrの耐酸性試験結果は0.95%、サンプルqの耐酸性試験結果は0.90%と小さな値であるのに対して、X1とX2を結ぶ直線よりもすぐ下側に位置しているサンプルa、b、cの耐酸性試験結果は、順に3.82、2,78、3.93とサンプルrおよびqと比較して非常に大きく、直線X1とX2を結ぶ直線付近で急激に耐酸性の試験結果は変化していることがわかる。 Further, according to FIG. 4, the acid resistance test result of the sample r is 0.95%, and the acid resistance test result of the sample q is 0.90%, which are small values, whereas the straight line connecting X1 and X2 The acid resistance test results of the samples a, b, and c located immediately below are 3.82, 2,78, 3.93, which are very large compared to the samples r and q, and the straight line X1. It can be seen that the acid resistance test results change rapidly near the straight line connecting X2.
したがって、耐アルカリ性と耐酸性において共に優れた特性を有する本封着ガラスは、従来のガラスと比較しても顕著な効果を有している。 Therefore, the sealed glass having excellent properties in both alkali resistance and acid resistance has a remarkable effect as compared with the conventional glass.
点I、II、III、IVそれぞれのSiO2、CaOおよびAl2O3の含有モル比に囲まれた領域内におけるSiO2のSi元素の半分以下をSi元素と同じ14族であるGeに置き換えても本封着ガラスと同様の耐アルカリ性及び耐酸性を有する。
In the region surrounded by the molar ratios of SiO 2 , CaO and Al 2 O 3 at points I, II, III and IV, less than half of the Si element of SiO 2 is replaced with Ge, which is the
点I、II、III、IVそれぞれのSiO2、CaOおよびAl2O3の含有モル比に囲まれた領域内におけるCaOのCa元素の半分以下をCa元素と同じ2価の価数を有する金属イオンの酸化物MO(ここでMはBe,Mg,Ba,Sr,Mn,Ni,Cu,Zn,Cd,Sn,Pbから選ばれる少なくとも1つ以上の元素)に置き換えても本封着ガラスと同様の耐アルカリ性及び耐酸性を有する。 Metals having the same divalent valence as the Ca element in less than half of the Ca element of CaO in the region surrounded by the molar ratios of SiO 2 , CaO and Al 2 O 3 at points I, II, III and IV respectively. Even if it is replaced with an ion oxide MO (where M is at least one element selected from Be, Mg, Ba, Sr, Mn, Ni, Cu, Zn, Cd, Sn, and Pb), the sealed glass can be used. It has similar alkali resistance and acid resistance.
点I、II、III、IVそれぞれのSiO2、CaOおよびAl2O3の含有モル比に囲まれた領域内におけるAl2O3のAl元素の半分以下をAl元素と同じ3価の価数を有する酸化物X2O3(ここでXはGa,B,In,Sb,Bi,Sc,Y,Fe,ランタノイドから選ばれる少なくとも1つ以上の元素)に置き換えても本封着ガラスと同様の耐アルカリ性及び耐酸性を有する。 Less than half of the Al element of Al 2 O 3 in the region surrounded by the molar ratio of SiO 2 , Ca O and Al 2 O 3 of each of points I, II, III and IV is the same trivalent valence as the Al element. Even if it is replaced with an oxide X 2 O 3 having (where X is at least one or more elements selected from Ga, B, In, Sb, Bi, Sc, Y, Fe, and lanthanoids) Has alkali resistance and acid resistance.
製作したガラスの線膨張係数を、熱機械分析装置:Thermoplus TMA8310(Rigaku製、JIS R1618準拠)を用いて測定した。その結果を下記表3に示す。 The linear expansion coefficient of the manufactured glass was measured using a thermomechanical analyzer: Thermoplus TMA8310 (manufactured by Rigaku, JIS R1618 compliant). The results are shown in Table 3 below.
10:テフロン内筒密閉容器
11:テフロン糸
12:テフロン内筒
13:浸漬液
14:テストサンプル
10: Teflon inner cylinder closed container 11: Teflon thread 12: Teflon inner cylinder 13: immersion liquid 14: test sample
Claims (4)
当該封着ガラスはSiO 2 、CaOおよびAl 2 O 3 の3成分のみからなり、
SiO2、CaOおよびAl2O3の含有モル比が、3元系状態図における
(I)(SiO2:CaO:Al2O3)=(57.0:40.0:3.0)
(II)(SiO2:CaO:Al2O3)=(53.5:40.0:6.5)
(III)(SiO2:CaO:Al2O3)=(60.5:33.0:6.5)
(IV)(SiO2:CaO:Al2O3)=(64.0:33.0:3.0)の4点に囲まれている範囲であることを特徴とする封着ガラス。 It ’s a ceramic sealing glass.
The sealed glass consists of only three components , SiO 2 , CaO and Al 2 O 3 .
The molar ratio of S iO 2 , CaO and Al 2 O 3 is (I) (SiO 2 : CaO: Al 2 O 3 ) = (57.0: 40.0: 3.0) in the ternary phase diagram.
(II) (SiO 2 : CaO: Al 2O 3 ) = (53.5: 40.0: 6.5)
(III) (SiO 2 : CaO: Al 2O 3 ) = (60.5: 33.0: 6.5)
(IV) A sealing glass having a range surrounded by four points (SiO 2 : CaO: Al 2O 3 ) = (64.0: 33.0: 3.0).
当該ゼオライト分離膜は、支持体となるセラミック多孔質管の管端を封止または膜モジュールに固定するためのセラミック接合部材を有し、
前記セラミック多孔質管と前記セラミック接合部材は、請求項1~3のいずれか1つに記載の封着ガラスによって接合されていることを特徴とするゼオライト分離膜。
A zeolite separation membrane in which a zeolite layer is formed on the surface of a ceramic porous tube.
The zeolite separation membrane has a ceramic bonding member for sealing or fixing the tube end of the ceramic porous tube to be a support to the membrane module.
A zeolite separation membrane characterized in that the ceramic porous tube and the ceramic bonding member are bonded by the sealing glass according to any one of claims 1 to 3.
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