JPH0971481A - Ceramic porous support - Google Patents
Ceramic porous supportInfo
- Publication number
- JPH0971481A JPH0971481A JP7227686A JP22768695A JPH0971481A JP H0971481 A JPH0971481 A JP H0971481A JP 7227686 A JP7227686 A JP 7227686A JP 22768695 A JP22768695 A JP 22768695A JP H0971481 A JPH0971481 A JP H0971481A
- Authority
- JP
- Japan
- Prior art keywords
- crystals
- porous support
- ceramic porous
- mullite
- diameter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Filtering Materials (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ゼオライト膜形成
用セラミックス多孔質支持体に関する。TECHNICAL FIELD The present invention relates to a porous ceramic support for forming a zeolite film.
【０００２】[0002]
【従来の技術】近年、大気汚染の一因である一酸化炭素
の増加など環境汚染が深刻な問題となっている。そこ
で、例えば、米国ではガソリンにエタノールを添加し
て、完全燃焼を促し、一酸化炭素を低減する規制の導入
が検討されている。しかしながら、エタノールの添加に
より、ガソリンの完全燃焼促進の効果は奏されるもの
の、エタノール中に含まれる水分がエンジンのノッキン
グの原因となるという問題点がある。2. Description of the Related Art In recent years, environmental pollution such as an increase in carbon monoxide, which is one of the causes of air pollution, has become a serious problem. Therefore, for example, in the United States, introduction of regulations for adding ethanol to gasoline to promote complete combustion and reduce carbon monoxide is under study. However, although the addition of ethanol has the effect of promoting complete combustion of gasoline, there is a problem that water contained in ethanol causes knocking of the engine.
【０００３】このため、エタノールの脱水が必要となる
が、従来よリ行われている蒸留法では処理能力が低く、
コストが高く、更に、共沸混合物等の分離が不可能であ
るという欠点があり、近年、脱水能力が高く、コストが
安いＰＶ法（パーベーパレーション法）が注目されてい
る。この方法は、特定の成分のみを透過する隔膜を隔て
て１次側に液体混合物を供給し、２次側を減圧状態とし
て、特定の成分を隔膜に選択的に溶解・拡散させて透過
させ、２次側に蒸気として取リ出す方法である。このＰ
Ｖ法の問題点としては、従来隔膜として多く用いられて
いる高分子有機膜は、耐熱性が低く、使用される液に含
まれる酸やアルカリ等の不純物が膜寿命に影響を与え、
分離係数の低下や透過量の減少などの問題が生じること
が挙げられる。For this reason, it is necessary to dehydrate ethanol, but the conventional distillation method has a low processing capacity,
The PV method (pervaporation method), which has a high cost and has a drawback that the azeotropic mixture and the like cannot be separated, has a high dewatering capacity and a low cost in recent years. In this method, a liquid mixture is supplied to the primary side across a septum that transmits only a specific component, and the secondary side is depressurized to selectively dissolve and diffuse the specific component into the septum, This is a method of extracting as steam to the secondary side. This P
The problem with the V method is that polymer organic membranes that have been widely used as conventional diaphragms have low heat resistance, and impurities such as acids and alkalis contained in the liquid used affect the membrane life.
Problems such as a reduction in the separation coefficient and a reduction in the permeation amount may occur.
【０００４】そこで、高分子有機膜に代えて、ゼオライ
ト膜等の微細孔を有する無機膜を用いる方法が検討され
ている。斯かる方法では、通常、ゼオライト膜を適当な
支持体上に形成することが必要であり、従来は、支持体
として、アルミナ製のセラミックス多孔質体が用いられ
ている。しかしながら、ゼオライト膜を用いる方法にお
いて、被処理物の透過量、分離係数等を良好とするため
には、支持体の細孔径等を正確に制御することが必要で
あり、アルミナセラミックスでは、細孔径等を制御する
ためには微細な原料粉末の使用が不可欠となり、このよ
うな微細な原料粉末の使用により生産コス卜が高くなる
という難点がある。Therefore, a method of using an inorganic membrane having fine pores such as a zeolite membrane instead of the polymer organic membrane has been studied. In such a method, it is usually necessary to form a zeolite membrane on an appropriate support, and conventionally, a ceramic porous body made of alumina is used as the support. However, in the method using a zeolite membrane, in order to improve the permeation amount and separation coefficient of the object to be treated, it is necessary to accurately control the pore size of the support. The use of a fine raw material powder is indispensable for controlling the above-mentioned problems, and the use of such a fine raw material powder raises the problem of increasing the production cost.
【０００５】[0005]
【発明が解決しようとする課題】本発明の主な目的は、
ゼオライト膜の支持体として有用であり、しかも安価に
製造し得るセラミックス多孔質支持体を提供することで
ある。The main object of the present invention is to:
It is an object of the present invention to provide a ceramic porous support which is useful as a support for a zeolite membrane and can be manufactured at low cost.
【０００６】[0006]
【課題を解決するための手段】本発明者は、上記した従
来技術の問題点に鑑みて、鋭意研究を重ねた結果、主と
してムライト結晶からなる焼結体、又は主としてムライ
ト結晶及びアルミナ結晶の混合晶からなる焼結体であっ
て、Ａｌ2Ｏ3／ＳｉＯ2組成、平均結晶粒径、アスペク
ト比、気孔率、及び細孔径の全ての条件について同時に
特定範囲の値になるように制御したセラミックス多孔質
材料は、ゼオライト膜の支持体とした場合に、良好なゼ
オライト膜を形成することができ、しかもこの様な特定
条件を満足する焼結体は、アルミナと比べて製造が容易
であり、安価に製造できることを見出した。そして、該
支持体にセラミックス膜を形成したものを、被処理物か
ら特定成分を分離するための隔膜として用いた場合に
は、透過量、分離係数等が良好で、耐食性、耐熱性など
も優れているため、各種の用途に有効に使用し得るもの
となることを見出し、ここに本発明を完成するに至っ
た。DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies in view of the above-mentioned problems of the prior art, and as a result, a sintered body mainly composed of mullite crystals or a mixture of mainly mullite crystals and alumina crystals. Sintered body consisting of crystals, ceramics controlled to have values within a specific range for all conditions of Al 2 O 3 / SiO 2 composition, average crystal grain size, aspect ratio, porosity, and pore size The porous material, when used as a support for the zeolite membrane, can form a good zeolite membrane, and a sintered body that satisfies such specific conditions is easier to manufacture than alumina, It was found that it can be manufactured at low cost. When a ceramic film formed on the support is used as a diaphragm for separating a specific component from the object to be processed, the permeation amount, the separation coefficient, etc. are good, and the corrosion resistance, heat resistance, etc. are excellent. Therefore, they have found that they can be effectively used for various purposes, and have completed the present invention.
【０００７】即ち、本発明は、下記のゼオライト膜形成
用セラミックス多孔質支持体に係る。That is, the present invention relates to the following ceramic porous support for forming a zeolite film.
【０００８】（１）主としてムライト結晶からなる焼結
体、又は主としてムライト結晶及びアルミナ結晶の混合
晶からなる焼結体であり、（２）Ａｌ2Ｏ3／ＳｉＯ2重
量比が６０／４０〜７８／２２、（３）Ａｌ2Ｏ3及びＳ
ｉＯ2の合計量が９２重量％以上、（４）平均結晶粒径
が０．５〜３μｍ、（５）細孔径のモード径及び５０％
径がそれぞれ０．１〜２μｍ、（６）気孔率が３５〜５
０％、（７）ムライト結晶の平均アスペクト比が２〜
７、であることを特徴とするゼオライト膜形成用セラミ
ックス多孔質支持体。(1) A sintered body mainly composed of mullite crystals, or a sintered body mainly composed of a mixed crystal of mullite crystals and alumina crystals, and (2) an Al 2 O 3 / SiO 2 weight ratio of 60/40 to. 78/22, (3) Al 2 O 3 and S
The total amount of iO 2 is 92% by weight or more, (4) the average crystal grain size is 0.5 to 3 μm, (5) the mode diameter of the pore diameter and 50%
Diameter is 0.1 to 2 μm, (6) Porosity is 35 to 5
0%, (7) Mullite crystals have an average aspect ratio of 2
7. A ceramic porous support for forming a zeolite film, characterized in that
【０００９】[0009]
【発明の実施の形態】以下に、本発明のセラミックス多
孔質支持体が満足すべき各要件について詳細に説明す
る。BEST MODE FOR CARRYING OUT THE INVENTION Each requirement to be satisfied by the ceramic porous support of the present invention will be described in detail below.
【００１０】（１）主としてムライト結晶からなる焼結
体、又は主としてムライト結晶及びアルミナ結晶の混合
晶からなる焼結体であること。(1) A sintered body mainly composed of mullite crystals or a sintered body mainly composed of mixed crystals of mullite crystals and alumina crystals.
【００１１】本発明のセラミックス多孔質支持体は、主
としてムライト結晶からなる焼結体、又はムライト結晶
及びアルミナ結晶の混合晶からなる焼結体であることが
必要である。ムライト結晶及びアルミナ結晶は、化学的
に安定で、耐食性、耐熱性に優れたものであり、しか
も、ムライト結晶、又はムライト結晶及びアルミナ結晶
の混合晶の場合、アルミナ結晶単体と比べて、焼成温度
に対して粒成長速度が遅く、細孔径の制御が容易であ
る。このため、ムライト結晶からなる焼結体、又はムラ
イト結晶及びアルミナ結晶の混合晶からなる焼結体で
は、目的とする細孔径等の条件を満足する焼結体を容易
に得ることができる。The ceramic porous support of the present invention must be a sintered body mainly composed of mullite crystals or a mixed crystal of mullite crystals and alumina crystals. Mullite crystals and alumina crystals are chemically stable, and have excellent corrosion resistance and heat resistance, and in the case of mullite crystals or mixed crystals of mullite crystals and alumina crystals, the firing temperature is higher than that of alumina crystals alone. On the other hand, the grain growth rate is slow and the control of the pore size is easy. Therefore, in the sintered body composed of mullite crystals or the sintered body composed of mixed crystals of mullite crystals and alumina crystals, it is possible to easily obtain a sintered body that satisfies the desired conditions such as the pore diameter.
【００１２】尚、本発明のセラミックス多孔質支持体
は、主としてムライト結晶からなる焼結体、又は主とし
てムライト結晶及びアルミナ結晶の混合晶からなる焼結
体であるが、具体的には、Ｘ線回折により回折角２０〜
４５゜で測定したムライトの（２１０）面(M(210))、ア
ルミナの（１１３）面(A(113))、クリストバライトの
（１０１）面(C(101))の各面の回折ピーク強度比が下記
の条件を満たすことが適当である。The ceramic porous support of the present invention is a sintered body mainly composed of mullite crystals or a sintered body mainly composed of a mixed crystal of mullite crystals and alumina crystals. Diffraction angle of 20 ~
Diffraction peak intensities of mullite (210) plane (M (210)), alumina (113) plane (A (113)), and cristobalite (101) plane (C (101)) measured at 45 ° It is appropriate that the ratio satisfies the following conditions.
【００１３】M(210)/(M(210)+A(113)+C(101))≧0.4 A(113)/(M(210)+A(113)+C(101))≦0.5 C(101)/(M(210)+A(113)+C(101))≦0.1 上記回折ピーク強度比のうちで、A(113)/(M(210)+A(11
3)+C(101))が０．５を超える場合は、アルミナ結晶量が
多くなり過ぎて、ムライト結晶とアルミナ結晶との熱膨
張差により、粒界に生成するマイクロクラックが増加
し、細孔径が大きくなるので好ましくない。また、C(10
1)/(M(210)+A(113)+C(101))が０．１を超える場合に
は、多孔質支持体中のクリストバライト量が多くなり過
ぎて、焼成時の冷却過程で割れが発生し易く、また耐食
性の低下にもつながるので好ましくない。本発明では、
下記の条件を満たすことがより好ましい。M (210) / (M (210) + A (113) + C (101)) ≧ 0.4 A (113) / (M (210) + A (113) + C (101)) ≦ 0.5 C (101) / (M (210) + A (113) + C (101)) ≦ 0.1 Of the above diffraction peak intensity ratios, A (113) / (M (210) + A (11
When 3) + C (101)) is more than 0.5, the amount of alumina crystals becomes too large and the thermal expansion difference between the mullite crystals and the alumina crystals increases the number of microcracks generated at the grain boundaries, resulting in fine cracks. It is not preferable because the pore size becomes large. Also, C (10
If 1) / (M (210) + A (113) + C (101)) exceeds 0.1, the amount of cristobalite in the porous support becomes too large and cracks occur during the cooling process during firing. Is likely to occur and also leads to a decrease in corrosion resistance, which is not preferable. In the present invention,
It is more preferable to satisfy the following conditions.
【００１４】M(210)/(M(210)+A(113)+C(101))≧0.5 A(113)/(M(210)+A(113)+C(101))≦0.45 C(101)/(M(210)+A(113)+C(101))≦0.05 （２）Ａｌ2Ｏ3／ＳｉＯ2重量比が６０／４０〜７８／
２２であること。M (210) / (M (210) + A (113) + C (101)) ≧ 0.5 A (113) / (M (210) + A (113) + C (101)) ≦ 0.45 C (101) / (M (210) + A (113) + C (101)) ≦ 0.05 (2) Al 2 O 3 / SiO 2 weight ratio is 60/40 to 78 /
Must be 22.
【００１５】本発明においては、Ａｌ2Ｏ3／ＳｉＯ2重
量比が６０／４０〜７８／２２の範囲にあることが必要
であり、６２／３８〜７５／２５の範囲にあることが好
ましい。In the present invention, the Al 2 O 3 / SiO 2 weight ratio needs to be in the range of 60/40 to 78/22, preferably 62/38 to 75/25.
【００１６】Ａｌ2Ｏ3／ＳｉＯ2重量比が６０／４０を
下回るとシリカ系ガラス相が多くなって、耐食性が低下
するので好ましくない。一方、Ａｌ2Ｏ3／ＳｉＯ2重量
比が７８／２２を上回るとアルミナ結晶が増加し、ムラ
イト結晶粒径とアルミナ結晶粒径との違いから結晶粒径
分布が広くなり、不均一なゼオライト膜が形成され易
く、被処理物の透過量、分離係数等が低下し易いので好
ましくない。When the Al 2 O 3 / SiO 2 weight ratio is less than 60/40, the silica-based glass phase increases and the corrosion resistance decreases, which is not preferable. On the other hand, when the Al 2 O 3 / SiO 2 weight ratio exceeds 78/22, the number of alumina crystals increases, and the crystal grain size distribution becomes wide due to the difference between the mullite crystal grain size and the alumina crystal grain size, resulting in a non-uniform zeolite film. Are easily formed, and the permeation amount of the object to be processed, the separation coefficient, and the like are easily reduced, which is not preferable.
【００１７】（３）Ａｌ2Ｏ3及びＳｉＯ2の合計量が９
２重量％以上であること。(3) The total amount of Al 2 O 3 and SiO 2 is 9
Must be at least 2% by weight.
【００１８】本発明においては、Ａｌ2Ｏ3及びＳｉＯ2
の合計量が９２重量％以上であることが必要であり、９
５重量％以上であることが好ましい。これらの合計量が
９２重量％未満の場合には、不純物の増加により、ムラ
イト、アルミナ結晶以外の第２相の生成が起こり易く、
またアルカリ不純物量の増加により、アルカリ不純物が
ＳｉＯ2と反応してガラス相を形成し、ムライト結晶量
の減少とアルミナ結晶量の増加につながり、その結果、
耐食性が低下すると共に、焼結体の気孔率が低下して細
孔径が小さくなり過ぎる傾向にあるので好ましくない。In the present invention, Al 2 O 3 and SiO 2
It is necessary that the total amount of
It is preferably at least 5% by weight. If the total amount of these is less than 92% by weight, an increase in impurities easily causes the formation of a second phase other than mullite and alumina crystals,
Also, due to the increase in the amount of alkali impurities, the alkali impurities react with SiO 2 to form a glass phase, which leads to a decrease in the amount of mullite crystals and an increase in the amount of alumina crystals.
It is not preferable because the corrosion resistance is lowered and the porosity of the sintered body is lowered so that the pore size tends to be too small.
【００１９】（４）平均結晶粒径が０．５〜３μmであ
ること。(4) The average crystal grain size is 0.5 to 3 μm.
【００２０】本発明のセラミックス多孔質支持体では、
平均結晶粒径が０．５〜３μmであることが必要であ
り、０．５〜２μｍであることが好ましい。In the ceramic porous support of the present invention,
It is necessary that the average crystal grain size is 0.5 to 3 μm, and preferably 0.5 to 2 μm.
【００２１】平均結晶粒径が０．５μm未満の場合に
は、該支持体の細孔径が小さくなり過ぎて、透過量、分
離係数などが低下するので好ましくない。一方、結晶粒
径が３μｍを上回る場合には、該支持体の細孔径が大き
くなり、ゼオライト膜を形成する際に、膜を形成する成
分の結晶等が細孔に詰まり易く、透過量や分離係数が低
下し易いので好ましくない。If the average crystal grain size is less than 0.5 μm, the pore size of the support becomes too small and the permeation amount, the separation coefficient, etc. are reduced, which is not preferable. On the other hand, when the crystal grain size exceeds 3 μm, the pore size of the support becomes large, and when forming a zeolite membrane, the crystals of the components forming the membrane are likely to be clogged in the pores, and the permeation amount and separation This is not preferable because the coefficient tends to decrease.
【００２２】尚、本発明のセラミックス多孔質支持体に
おける平均結晶粒径は、結晶形状を円形状に換算した値
を用い、具体的には下記の方法で求める。The average crystal grain size in the ceramics porous support of the present invention is obtained by converting the crystal shape into a circular shape, specifically by the following method.
【００２３】まず、セラミックス多孔質支持体を鏡面に
仕上げ、０℃の１％ＨＦ溶液中で２４時間エッチングを
する。次いで、走査電子顕微鏡を用いて、結晶が１００
個以上観察できる倍率でエッチング面を観察し、写真撮
影を行なう。写真から結晶が占める面積（Ｓ）を求め、
その面積にある結晶数（ｎ）から、次式により、平均結
晶粒径を算出する。First, the ceramic porous support is mirror-finished and etched in a 1% HF solution at 0 ° C. for 24 hours. Then, using a scanning electron microscope, 100 crystals are obtained.
Observe the etched surface at a magnification that allows you to observe more than one, and take a photograph. Calculate the area (S) occupied by crystals from the photograph,
From the number of crystals (n) in the area, the average crystal grain size is calculated by the following formula.
【００２４】平均結晶粒径：Ｄ（μｍ）＝（Ｓ／π・
ｎ）0.5×１．５ （５）細孔径のモード径及び５０％径が、それぞれ０．
１〜２μmであること。Average crystal grain size: D (μm) = (S / π ·
n) 0.5 × 1.5 (5) The mode diameter of the pore diameter and the 50% diameter are 0.
Must be 1-2 μm.
【００２５】本発明のセラミックス多孔質支持体の細孔
径は、ＡＳＴＭ Ｆ３１６−８６に基づいて、媒体とし
てＦＣ−４３(パーフルオロカーボン)を用いて、バブル
ポイント法により測定する。従来から行われている細孔
径の測定法である水銀圧入法では、開気孔だけでなく閉
気孔も測定してしまうため、本発明のセラミックス多孔
質支持体の細孔径の測定には適さず、開気孔径のみを測
定できる上記バブルポイント法により細孔径の測定を行
う。The pore size of the ceramic porous support of the present invention is measured by the bubble point method based on ASTM F316-86 using FC-43 (perfluorocarbon) as a medium. In the mercury press-in method, which is a conventionally known method for measuring the pore diameter, since it measures not only open pores but also closed pores, it is not suitable for measuring the pore diameter of the ceramic porous support of the present invention, The pore diameter is measured by the bubble point method which can measure only the open pore diameter.
【００２６】この様にして求めた細孔径の５０％径と
は、細孔径累積分布曲線において、累積値が５０％を示
す細孔径であり、モード径とは細孔径累積分布曲線から
得られる細孔径のヒストグラムにおいて度数が一番高い
細孔径である。The 50% diameter of the pore diameter thus obtained is the pore diameter whose cumulative value shows 50% in the pore diameter cumulative distribution curve, and the mode diameter is the fine diameter obtained from the pore diameter cumulative distribution curve. It is the pore size with the highest frequency in the pore size histogram.
【００２７】本発明では、この様にして求めた細孔径の
モード径及び５０％径がそれぞれ０．１〜２μmである
ことが必要である。モード径及び５０％径が０．１μm
未満の場合は、ゼオライト膜との密着性が高くなりすぎ
て、被処理物の透過量、分離係数等が低下し易いので好
ましくない。また、２μmを超える場合は、形成するゼ
オライト膜にピンホールが発生し易くなり、更にゼオラ
イト膜の形成時に膜を構成する成分の結晶等が細孔に詰
まり易くなり、透過量、分離係数等の低下につながるの
で好ましくない。In the present invention, it is necessary that the mode diameter and the 50% diameter of the pore diameter thus obtained are 0.1 to 2 μm, respectively. Mode diameter and 50% diameter are 0.1 μm
If it is less than the above range, the adhesion to the zeolite membrane becomes too high, and the permeation amount of the object to be treated, the separation coefficient, etc. are likely to decrease, which is not preferable. On the other hand, when it exceeds 2 μm, pinholes are likely to be generated in the zeolite membrane to be formed, and further, crystals of the components constituting the membrane are likely to be clogged in the pores when the zeolite membrane is formed, and the permeation amount, the separation coefficient, etc. It is not preferable because it leads to a decrease.
【００２８】（６）気孔率が３５〜５０％であること。(6) Porosity is 35 to 50%.
【００２９】本発明の多孔質支持体において、気孔率
は、被処理物の透過量、分離係数等に影響し、更に、良
好なゼオライト膜を形成するためにも重要な要件とな
り、３５〜５０％の範囲とすることが必要である。In the porous support of the present invention, the porosity affects the permeation amount of the object to be treated, the separation coefficient and the like, and is an important requirement for forming a good zeolite membrane. It is necessary to set it in the range of%.
【００３０】気孔率が３５％未満の場合には、膜の密着
強度が弱くなって、膜の剥離や不均一性が生じたり、透
過量の低下が生じるので好ましくなく、一方、気孔率が
５０％を超える場合には、ゼオライト膜形成時に、膜の
構成成分の結晶が細孔に詰まり、透過量、分離係数等が
低下するので好ましくない。If the porosity is less than 35%, the adhesion strength of the film is weakened, peeling of the film or non-uniformity occurs, or the amount of permeation decreases, which is not preferable, while the porosity is 50%. If it exceeds%, the crystals of the constituent components of the membrane are clogged in the pores during the formation of the zeolite membrane, and the permeation amount, the separation coefficient, etc. are reduced, which is not preferable.
【００３１】（７）ムライト結晶の平均アスペクト比が
２〜７であること。(7) The average aspect ratio of the mullite crystal is 2 to 7.
【００３２】本発明の多孔質支持体では、ムライト結晶
の平均アスペクト比が２〜７の範囲にあることが必要で
あり、２．５〜６の範囲にあることが好ましい。平均ア
スペクト比が７を上回る場合には、該多孔質支持体上に
ゼオライト膜を形成すると、ムライト結晶１個について
形成される膜成分の結晶数が多くなりすぎて、被処理物
の拡散に対する抵抗が大きくなり、透過量、分離係数な
どの低下をきたすので好ましくない。In the porous support of the present invention, the average aspect ratio of mullite crystals needs to be in the range of 2 to 7, preferably 2.5 to 6. When the average aspect ratio exceeds 7, when a zeolite membrane is formed on the porous support, the number of crystal of the membrane component formed per one mullite crystal becomes too large, and the resistance to diffusion of the object to be treated is increased. Becomes large, and the permeation amount and the separation coefficient are lowered, which is not preferable.
【００３３】本発明では、平均アスペクト比の測定は、
平均結晶粒径の測定と同様に走査電子顕微鏡を用いて焼
結体のエッチング面を写真撮影して行ない、任意の２０
個のムライト結晶の長径と短径を測定し、長径／短径の
比をアスペクト比とし、２０個の平均値を平均アスペク
ト比とする。尚、平均アスペクト比の測定に先立って、
エネルギー分散型Ｘ線分光分析（ＥＤＸ）を行い、アル
ミニウム及びシリコン元素が同時に現れる結晶をムライ
ト結晶として同定する。In the present invention, the average aspect ratio is measured by
Photograph the etched surface of the sintered body using a scanning electron microscope in the same manner as the measurement of the average crystal grain size.
The major axis and minor axis of each mullite crystal are measured, the major axis / minor axis ratio is taken as the aspect ratio, and the average value of 20 is taken as the average aspect ratio. In addition, prior to the measurement of the average aspect ratio,
Energy dispersive X-ray spectroscopic analysis (EDX) is performed, and a crystal in which aluminum and silicon elements simultaneously appear is identified as a mullite crystal.
【００３４】本発明のセラミックス多孔質支持体は、上
記した（１）〜（７）の条件を同時に満足する焼結体で
あるが、更に、該焼結体における最大細孔径が５μｍ以
下であることが好ましい。最大細孔径が５μｍを上回る
場合には、ゼオライト膜を形成する際に、膜にピンホー
ルが生じやすく、また、膜の結晶成分が細孔に詰まっ
て、透過量、分離係数等が低下しやすいので好ましくな
い。最大細孔径は、２μｍ以下であることがより好まし
い。The ceramic porous support of the present invention is a sintered body which simultaneously satisfies the above-mentioned conditions (1) to (7), and further, the maximum pore diameter in the sintered body is 5 μm or less. It is preferable. If the maximum pore size exceeds 5 μm, pinholes are likely to be formed in the membrane when the zeolite membrane is formed, and the crystalline components of the membrane are clogged in the pores, and the permeation amount, separation coefficient, etc. are likely to decrease. It is not preferable. The maximum pore size is more preferably 2 μm or less.
【００３５】上記した本発明セラミックス多孔質支持体
は、常法に従って適宜製造できるが、その製造法の一例
を示すと以下の通りである。The above-mentioned ceramic porous support of the present invention can be appropriately manufactured by a conventional method, and an example of the manufacturing method is as follows.
【００３６】まず、凝集した二次粒子の平均粒子径が２
５〜３５μｍ程度の範囲にあるＡｌ2 Ｏ3 、カオリン等
の粘度鉱物を原料とし、これを所定のＡｌ2 Ｏ3 ／Ｓｉ
Ｏ2重量比となるように配合し、バインダー、分散剤等
を添加して、水、エチルアルコール等の溶媒中で、ボー
ルミル、アトリッションミル等の粉砕機を用いて、粉砕
粒度が１０〜１５μｍ程度となるように、湿式で粉砕、
混合、分散する。バインダー及び分散剤としては、通常
の焼結体の製造に用いるものを使用でき、バインダーの
具体例としては、ポリビニルアルコール（ＰＶＡ）、ワ
ックスエマルジョン、カルボキシメチルセルロース（Ｃ
ＭＣ）等を挙げることができる。分散剤の具体例として
は、スルホン酸アンモニウム塩、ピロリン酸ソーダ等を
挙げることができる。バインダー及び分散剤の添加量
は、成形方法などに応じて、目的とするセラミックス多
孔質支持体が形成されるように適宜決定すればよい。First, the average particle diameter of the aggregated secondary particles is 2
A viscous mineral such as Al 2 O 3 and kaolin in the range of 5 to 35 μm is used as a raw material, and this is used as a predetermined Al 2 O 3 / Si.
O 2 weight ratio is added, a binder, a dispersant, etc. are added, and in a solvent such as water or ethyl alcohol, a pulverizer having a pulverization particle size of 10 to 10 Pulverized by a wet method so that the size becomes about 15 μm,
Mix and disperse. As the binder and the dispersant, those used in the production of ordinary sintered bodies can be used, and specific examples of the binder include polyvinyl alcohol (PVA), wax emulsion, carboxymethyl cellulose (C
MC) and the like. Specific examples of the dispersant include ammonium sulfonate, sodium pyrophosphate, and the like. The addition amount of the binder and the dispersant may be appropriately determined depending on the molding method or the like so that the desired ceramic porous support is formed.
【００３７】この様にして得られた粉体をプレス成形、
鋳込み成形、押出成形等により所定の形状に成形し、Ａ
ｌ2 Ｏ3 ／ＳｉＯ2 重量比に応じて、１３００〜１６０
０℃程度、好ましくは１３５０〜１５５０℃程度で焼成
してムライト結晶を生じさせることによって、上記した
条件を満足するセラミックス多孔質支持体を得ることが
できる。The powder thus obtained is press-molded,
Molded into a predetermined shape by cast molding, extrusion molding, etc.
1 2 O 3 / SiO 2 depending on the weight ratio 1300-160
By firing at about 0 ° C., preferably at about 1350 to 1550 ° C. to generate mullite crystals, a ceramic porous support satisfying the above conditions can be obtained.
【００３８】本発明のセラミックス多孔質支持体は、こ
の表面にゼオライト膜を形成して、液体混合物、気体混
合物などの各種被処理物から特定成分を分離する為の隔
膜として用いられる。該支持体の大きさは、使用する装
置に応じて適宜設定することができ、該支持体の形状
も、使用する装置に応じて、角板、円筒状等の各種の形
状とすることができる。The ceramic porous support of the present invention is used as a diaphragm for forming a zeolite film on the surface thereof to separate a specific component from various kinds of objects to be treated such as liquid mixture and gas mixture. The size of the support can be appropriately set according to the device used, and the shape of the support can be various shapes such as a square plate and a cylinder depending on the device used. .
【００３９】該支持体上に形成するゼオライト膜として
は、公知の各種のもの、例えば、Ａ型、Ｙ型、グメリナ
イト、シリカライト、ＺＳＭ−５、ＺＳＭ−３５等のゼ
オライトを用いることができる。これらのゼオライト膜
を本発明の支持体上に形成する方法は、特に限定は無
く、水熱合成法、気相法等の公知の各種方法によればよ
い。例えば、Ａ型ゼオライト膜を水熱合成により形成す
るには、ケイ酸ナトリウム水溶液と、アルミン酸ナトリ
ウム水溶液又は水酸化ナトリウムと水酸化アルミニウム
の混合液とを室温で混合し、円筒状のガラス容器に仕込
み、これに、本発明の支持体を浸漬し、水熱合成により
膜形成を行えばよい。As the zeolite film formed on the support, various known ones, for example, A type, Y type, gmelinite, silicalite, ZSM-5, ZSM-35, etc. can be used. The method for forming these zeolite membranes on the support of the present invention is not particularly limited, and various known methods such as a hydrothermal synthesis method and a vapor phase method may be used. For example, to form an A-type zeolite membrane by hydrothermal synthesis, a sodium silicate aqueous solution and a sodium aluminate aqueous solution or a mixed solution of sodium hydroxide and aluminum hydroxide are mixed at room temperature and placed in a cylindrical glass container. A substrate may be charged, the support of the present invention may be dipped therein, and a film may be formed by hydrothermal synthesis.
【００４０】本発明の支持体上に形成するゼオライト膜
の膜厚は、特に限定されるものではないが、通常、５〜
１００μｍ程度とすればよい。The thickness of the zeolite membrane formed on the support of the present invention is not particularly limited, but usually 5 to 5
It may be about 100 μm.
【００４１】本発明のセラミックス多孔質支持体上に、
ゼオライト膜を形成した材料は、液体混合物、気体混合
物などの各種被処理物からの特定成分の分離のための隔
膜として用いた場合に、透過量、分離係数等が良好であ
り、例えば、ＰＶ法によるエタノール中に含まれる水分
の除去、アルコール中の有機液体の分離等の用途に極め
て有効に用いることができる。また、該支持体は、耐熱
性、耐食性等に優れているために耐用期間が長く、形成
できる膜の種類や、被処理物の種類も多いため、各種の
用途に広く用いることができる。更に、該支持体は、安
価に製造可能であり、極めて有用性が高いものである。On the ceramic porous support of the present invention,
The material forming the zeolite membrane has good permeation amount, separation coefficient, etc. when used as a membrane for separating a specific component from various kinds of objects to be treated such as a liquid mixture and a gas mixture. It can be very effectively used for applications such as removal of water contained in ethanol by ethanol and separation of organic liquid in alcohol. Further, since the support has excellent heat resistance, corrosion resistance, etc., it has a long service life, and since there are many kinds of films that can be formed and many kinds of objects to be processed, they can be widely used for various purposes. Further, the support can be manufactured at low cost and is extremely useful.
【００４２】[0042]
【実施例】以下、実施例を挙げて本発明を更に詳細に説
明する。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples.
【００４３】実施例１ 所定のＡｌ2 Ｏ3 ／ＳｉＯ2 重量比となるように二次粒
子の平均粒子径が２５〜３５μｍのＡｌ2 Ｏ3及びカオ
リン原料を配合し、さらにバインダーとしてのポリビニ
ルアルコールと分散剤としてのスルホン酸アンモニウム
塩を添加し、ボールミルとボールを用いて、水を溶媒と
して粉砕粒度が１０〜１５μｍになるように粉砕、混合
した。次いで、得られたスラリーを乾燥し、含水率が２
５％になるように調整して坏土とした。なお、バインダ
ー及び分散剤の配合量は成形に際して適度な可塑性が得
られるように適宜調整した。この坏土を用いて焼成後の
大きさが外径１０ｍｍ、内径７ｍｍ、長さ５０ｍｍの円
筒状となる様に、押し出し成形によリ成形し、乾燥した
後、１２５０〜１６５０℃で２時間焼成してムライト含
有のセラミックス多孔質支持体を得た。[0043] Polyvinyl alcohol as in Example 1 the average particle size of a given Al 2 O 3 / SiO 2 weight ratio so as to secondary particles blended with Al 2 O 3 and kaolin raw materials 25～35Myuemu, further binder And ammonium sulfonate as a dispersant were added, and the mixture was pulverized and mixed using a ball mill and a ball with water as a solvent so that the pulverized particle size was 10 to 15 μm. Then, the obtained slurry is dried so that the water content is 2
The kneaded material was adjusted to be 5%. The blending amounts of the binder and the dispersant were appropriately adjusted so that appropriate plasticity was obtained during molding. Using this kneaded material, it is re-formed by extrusion molding so that the size after firing is a cylinder having an outer diameter of 10 mm, an inner diameter of 7 mm, and a length of 50 mm, and after drying, it is fired at 1250 to 1650 ° C. for 2 hours. Thus, a ceramic porous support containing mullite was obtained.
【００４４】表１に、得られたセラミックス多孔質支持
体のＡｌ2 Ｏ3 ／ＳｉＯ2 重量比、及びＡｌ2 Ｏ3 とＳ
ｉＯ2の合計重量％を示す。また、表２及び表３に得ら
れたセラミックス多孔質支持体の結晶相、平均結晶粒
径、細孔径、気孔率及びムライト結晶の平均アスペクト
比を示す。Ｎｏ．１〜５の試料は、本発明の要件を全て
満足するセラミックス多孔質支持体であり、Ｎｏ．６〜
９の試料は、本発明の要件の少なくとも１つを満たして
いない比較品である。Table 1 shows the Al 2 O 3 / SiO 2 weight ratio of the obtained ceramic porous support, and the Al 2 O 3 and S ratios.
The total weight% of iO 2 is shown. Tables 2 and 3 show the crystal phase, average crystal grain size, pore size, porosity, and average aspect ratio of mullite crystals of the obtained ceramic porous support. No. The samples Nos. 1 to 5 are ceramic porous supports satisfying all the requirements of the present invention, and No. 6 ~
Sample 9 is a comparative product that does not meet at least one of the requirements of the invention.
【００４５】次いで、Ｈ2Ｏ／Ｎａ2Ｏ＝５５、Ｎａ2Ｏ
／ＳｉＯ2＝１、ＳｉＯ2／Ａｌ2Ｏ3＝２の組成（モル
比）になるようにアルミン酸ナトリウムとケイ酸ナトリ
ウム水溶液を混合し、これを用いて、上記各支持体の外
表面に、１００℃で３時間水熱合成を行ない、Ａ型ゼオ
ライト膜を形成した。形成された膜の状態を表３に示
す。Then, H 2 O / Na 2 O = 55, Na 2 O
/ SiO 2 = 1 and SiO 2 / Al 2 O 3 = 2 so that the composition (molar ratio) of sodium aluminate and sodium silicate aqueous solution are mixed, and by using this, on the outer surface of each support Hydrothermal synthesis was performed at 100 ° C. for 3 hours to form an A-type zeolite membrane. Table 3 shows the state of the formed film.
【００４６】[0046]
【表１】 [Table 1]
【００４７】[0047]
【表２】 [Table 2]
【００４８】[0048]
【表３】 [Table 3]
【００４９】実施例２ 実施例１においてゼオライト膜を形成した試料の内で、
膜状態が良好であったＮｏ．１〜５及び９の試料を隔膜
として用いて、含水エタノール中の水分離試験を行っ
た。被処理エタノールとしては、表３に示す各含水率の
ものを用いた。Example 2 Among the samples having the zeolite membrane formed in Example 1,
The film condition was good. Using the samples 1 to 5 and 9 as a diaphragm, a water separation test in hydrous ethanol was conducted. As the ethanol to be treated, those having water contents shown in Table 3 were used.
【００５０】試験方法は、被処理エタノールの温度を５
０℃として、円筒状の試料の外側に供給し、円筒の内
部、即ち、二次側温度を−３０℃、二次側真空度を１．
４トールとして、透過量及び分離係数を求めた。The test method is that the temperature of the ethanol to be treated is 5
The sample is supplied to the outside of a cylindrical sample at 0 ° C., and the inside of the cylinder, that is, the secondary side temperature is −30 ° C. and the secondary side vacuum degree is 1.
The permeation amount and the separation coefficient were determined as 4 Torr.
【００５１】透過量は、単位時間当たりの単位膜面積当
たりの透過した水重量で示し、分離係数αは、下記式に
より求めた。The permeation amount is represented by the weight of water permeated per unit membrane area per unit time, and the separation coefficient α was obtained by the following formula.
【００５２】 分離係数α＝（Ｘａ／Ｘｂ）×（Ｙｂ／Ｙａ） Ｘａ：被処理エタノール中の水の重量分率 Ｘｂ：被処理エタノール中のエタノールの重量分率 Ｙａ：処理後エタノール中の水の重量分率 Ｙｂ：処理後エタノール中のエタノールの重量分率 結果を下記表４に示す。Separation coefficient α = (Xa / Xb) × (Yb / Ya) Xa: Weight fraction of water in ethanol to be treated Xb: Weight fraction of ethanol in ethanol to be treated Ya: Water in ethanol after treatment Weight fraction of Yb: The weight fraction of ethanol in the ethanol after treatment is shown in Table 4 below.
【００５３】[0053]
【表４】 [Table 4]
【００５４】以上の結果から明らかな様に、本発明の支
持体上にＡ型ゼオライト膜をコーティングした試料で
は、エタノール中の水分離に用いた場合に透過量が１．
８以上、分離係数αが６５０以上と優れた性能を示した
のに対して、本発明の条件を満足しない支持体であるＮ
ｏ．９の試料では、透過量及び分離係数が共に劣るもの
となった。As is clear from the above results, the sample of the present invention coated with the A-type zeolite membrane has a permeation amount of 1. when used for separating water in ethanol.
8 or more, and the separation coefficient α was 650 or more, which showed excellent performance, while N which is a support which does not satisfy the conditions of the present invention.
o. In the sample No. 9, the permeation amount and the separation coefficient were both poor.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 乾 一代 大阪府堺市遠里小野町３丁２番24号 株式 会社ニッカトー内 (72)発明者 河波 利夫 大阪府堺市遠里小野町３丁２番24号 株式 会社ニッカトー内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ichidai 3-2-24 Tori Ono-cho, Sakai City, Osaka Prefecture Nikkato Co., Ltd. (72) Inventor Toshio Kawanami 3 Tonori Ono-cho, Sakai City, Osaka Prefecture No. 2-24 In Nikkato Co., Ltd.
Claims (2)
体、又は主としてムライト結晶及びアルミナ結晶の混合
晶からなる焼結体であり、（２）Ａｌ2Ｏ3／ＳｉＯ2重
量比が６０／４０〜７８／２２、（３）Ａｌ2Ｏ3及びＳ
ｉＯ2の合計量が９２重量％以上、（４）平均結晶粒径
が０．５〜３μｍ、（５）細孔径のモード径及び５０％
径がそれぞれ０．１〜２μｍ、（６）気孔率が３５〜５
０％、（７）ムライト結晶の平均アスペクト比が２〜
７、であることを特徴とするゼオライト膜形成用セラミ
ックス多孔質支持体。(1) A sintered body mainly composed of mullite crystals, or a sintered body mainly composed of mixed crystals of mullite crystals and alumina crystals, (2) Al 2 O 3 / SiO 2 weight ratio of 60 /. 40-78 / 22, (3) Al 2 O 3 and S
The total amount of iO 2 is 92% by weight or more, (4) the average crystal grain size is 0.5 to 3 μm, (5) the mode diameter of the pore diameter and 50%
Diameter is 0.1 to 2 μm, (6) Porosity is 35 to 5
0%, (7) Mullite crystals have an average aspect ratio of 2
7. A ceramic porous support for forming a zeolite film, characterized in that
記載のセラミックス多孔質支持体。2. The ceramic porous support according to claim 1, which has a maximum pore diameter of 5 μm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22768695A JP4304381B2 (en) | 1995-09-05 | 1995-09-05 | Ceramic porous support |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22768695A JP4304381B2 (en) | 1995-09-05 | 1995-09-05 | Ceramic porous support |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0971481A true JPH0971481A (en) | 1997-03-18 |
| JP4304381B2 JP4304381B2 (en) | 2009-07-29 |
Family
ID=16864752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22768695A Expired - Fee Related JP4304381B2 (en) | 1995-09-05 | 1995-09-05 | Ceramic porous support |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4304381B2 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002533216A (en) * | 1998-12-30 | 2002-10-08 | コーニング インコーポレイテッド | Zeolite membrane and method for producing the same |
| JP2004202399A (en) * | 2002-12-25 | 2004-07-22 | Kyocera Corp | Ceramic porous member, production method thereof, and ceramic filter using the same |
| WO2004073841A1 (en) * | 2003-02-21 | 2004-09-02 | Bussan Nanotech Research Institute, Inc. | Method for concentrating water-soluble organic material |
| JP2006212551A (en) * | 2005-02-04 | 2006-08-17 | Hitachi Zosen Corp | Filter member and its manufacturing method |
| JP2007112678A (en) * | 2005-10-21 | 2007-05-10 | Nitsukatoo:Kk | Alumina substrate tube for separation film and its manufacturing method |
| JP2008094664A (en) * | 2006-10-12 | 2008-04-24 | Nitsukatoo:Kk | Alumina substrate tube for separation film and method of manufacturing the same |
| JP2008138114A (en) * | 2006-12-04 | 2008-06-19 | Denso Corp | Water separator, and fuel feeder for internal combustion engine |
| JP2009249204A (en) * | 2008-04-02 | 2009-10-29 | Nikkato:Kk | Substrate tube for one end closed type zeolite membrane |
| JP2009292709A (en) * | 2008-06-09 | 2009-12-17 | Tokyo Yogyo Co Ltd | Silicon carbide porous body |
| US11857929B2 (en) | 2018-09-28 | 2024-01-02 | Ngk Insulators, Ltd. | Support, zeolite membrane complex, method of producing zeolite membrane complex, and separation method |
-
1995
- 1995-09-05 JP JP22768695A patent/JP4304381B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002533216A (en) * | 1998-12-30 | 2002-10-08 | コーニング インコーポレイテッド | Zeolite membrane and method for producing the same |
| JP2004202399A (en) * | 2002-12-25 | 2004-07-22 | Kyocera Corp | Ceramic porous member, production method thereof, and ceramic filter using the same |
| WO2004073841A1 (en) * | 2003-02-21 | 2004-09-02 | Bussan Nanotech Research Institute, Inc. | Method for concentrating water-soluble organic material |
| US7594981B2 (en) | 2003-02-21 | 2009-09-29 | Mitsubishi Chemical Corporation | Method for concentrating water-soluble organic material |
| JP2006212551A (en) * | 2005-02-04 | 2006-08-17 | Hitachi Zosen Corp | Filter member and its manufacturing method |
| JP2007112678A (en) * | 2005-10-21 | 2007-05-10 | Nitsukatoo:Kk | Alumina substrate tube for separation film and its manufacturing method |
| JP4724529B2 (en) * | 2005-10-21 | 2011-07-13 | 株式会社ニッカトー | Alumina substrate tube for separation membrane and method for producing the same |
| JP2008094664A (en) * | 2006-10-12 | 2008-04-24 | Nitsukatoo:Kk | Alumina substrate tube for separation film and method of manufacturing the same |
| JP2008138114A (en) * | 2006-12-04 | 2008-06-19 | Denso Corp | Water separator, and fuel feeder for internal combustion engine |
| JP2009249204A (en) * | 2008-04-02 | 2009-10-29 | Nikkato:Kk | Substrate tube for one end closed type zeolite membrane |
| JP2009292709A (en) * | 2008-06-09 | 2009-12-17 | Tokyo Yogyo Co Ltd | Silicon carbide porous body |
| US11857929B2 (en) | 2018-09-28 | 2024-01-02 | Ngk Insulators, Ltd. | Support, zeolite membrane complex, method of producing zeolite membrane complex, and separation method |
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| Publication number | Publication date |
|---|---|
| JP4304381B2 (en) | 2009-07-29 |
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