JP2005344257A - Aluminous fiber, method for producing the same and use - Google Patents
Aluminous fiber, method for producing the same and use Download PDFInfo
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- JP2005344257A JP2005344257A JP2004167924A JP2004167924A JP2005344257A JP 2005344257 A JP2005344257 A JP 2005344257A JP 2004167924 A JP2004167924 A JP 2004167924A JP 2004167924 A JP2004167924 A JP 2004167924A JP 2005344257 A JP2005344257 A JP 2005344257A
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- 239000000835 fiber Substances 0.000 title claims abstract description 83
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 64
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 23
- 239000003463 adsorbent Substances 0.000 claims abstract description 21
- 238000009987 spinning Methods 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 18
- 229910052596 spinel Inorganic materials 0.000 claims description 17
- 239000011029 spinel Substances 0.000 claims description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 239000008119 colloidal silica Substances 0.000 claims description 8
- -1 Aluminum oxychloride Chemical compound 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 238000000465 moulding Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract 3
- 238000000034 method Methods 0.000 description 12
- 238000010304 firing Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 150000002013 dioxins Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 230000004075 alteration Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910018125 Al-Si Inorganic materials 0.000 description 2
- 229910018520 Al—Si Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Abstract
Description
本発明は、アルミナ質繊維、その製造方法及び用途に関する。 The present invention relates to an alumina fiber, a production method thereof, and an application.
触媒担体を繊維状とすれば、嵩密度を低くすることができるのでガスの透過性が高くなり、ガスの低温燃焼用触媒担体として有利となる。また、比表面積の大きな繊維はダイオキシン類等の環境汚染物質の吸着能力に優れるので、比表面積の大きなセラミック繊維が要望されている。この要望を満たすべく特許文献１など提案されているが、この方法は、特定の曇点を有する表面活性剤を紡糸原液に配合するものであるので、紡糸原液のチキソトロピー性が高くなり、シェアをかけると見かけ粘度が低下するなどの現象が顕著となるため、特殊な紡糸方式しか適用できないといった問題があった。しかも、紡糸原液の調製が複雑であるため、大量生産には不向きであった。
本発明の目的は、例えば触媒担体、吸着材等として好適な比表面積の大きなアルミナ質繊維、その製造方法並びにそれを用いた繊維状触媒担体、繊維状吸着材及びフィルターを提供することである。本発明の目的は、特定紡糸原液を調製し、それを繊維化した後、特定条件で焼成して少なくとも繊維表面をスピネル型結晶で変質することによって達成することができる。 An object of the present invention is to provide an alumina fiber having a large specific surface area suitable as, for example, a catalyst carrier and an adsorbent, a method for producing the same, and a fibrous catalyst carrier, a fibrous adsorbent and a filter using the same. The object of the present invention can be achieved by preparing a specific spinning dope, fiberizing it, and firing it under specific conditions to alter at least the fiber surface with spinel crystals.
本発明は、アルミナ成分が６０〜１００質量％、シリカ成分が０〜４０質量％、比表面積が１０〜２５０ｍ２／ｇのアルミナ質繊維からなり、少なくとも繊維表面がスピネル型結晶で変質されていることを特徴とするアルミナ質繊維である。また、本発明は、上記アルミナ質繊維からなることを特徴とする繊維状触媒担体又は繊維状吸着材であり、この繊維状吸着材の成形物からなることを特徴とするフィルターである。 The present invention is composed of alumina fibers having an alumina component of 60 to 100% by mass, a silica component of 0 to 40% by mass, and a specific surface area of 10 to 250 m 2 / g, and at least the fiber surface is altered by spinel crystals. This is an alumina fiber. Further, the present invention is a fibrous catalyst carrier or a fibrous adsorbent comprising the above-mentioned alumina fiber, and a filter comprising a molded product of this fibrous adsorbent.
さらに、本発明は、オキシ塩化アルミニウムと、コロイダルシリカと、紡糸助剤としてポリビニルアルコール、ポリエチレンオキサイド及びポリエチレングリコールから選ばれた少なくとも一種とを、アルミナ成分とシリカ成分の合計１００質量部に対してアルミナ分を６０質量部以上（１００を含む）、シリカ分を４０質量部以下（０を含む）、紡糸助剤を３〜１８質量部となるよう混合して紡糸原液を調製し、これを紡糸した後、毎分２〜５０℃の速度で７００〜１１５０℃まで昇温し、この温度で保持して少なくとも繊維表面をスピネル型結晶で変質させることを特徴とするアルミナ質繊維の製造方法である。 Furthermore, the present invention provides an aluminum oxychloride, colloidal silica, and at least one selected from polyvinyl alcohol, polyethylene oxide and polyethylene glycol as a spinning aid, with respect to a total of 100 parts by mass of an alumina component and a silica component. A spinning stock solution was prepared by mixing the mixture so that the amount was 60 parts by mass or more (including 100), the silica content was 40 parts by mass or less (including 0), and the spinning aid was 3 to 18 parts by mass. Thereafter, the temperature is raised to 700 to 1150 ° C. at a rate of 2 to 50 ° C. per minute, and kept at this temperature, and at least the surface of the fiber is denatured by spinel crystals.
本発明によれば、比表面積が１０〜２５０ｍ２／ｇのアルミナ質繊維とその製造方法が提供される。また、ガスの低温燃焼が可能で、耐熱性・耐薬品性に優れた繊維状触媒担体が提供される。さらには、ダイオキシン類等の環境汚染物質の吸着能力と耐熱性・耐薬品性とに優れた繊維状吸着材及びこの吸着材で構成されたフィルターが提供される。 According to the present invention, an alumina fiber having a specific surface area of 10 to 250 m 2 / g and a method for producing the same are provided. Further, a fibrous catalyst carrier capable of low temperature combustion of gas and having excellent heat resistance and chemical resistance is provided. Furthermore, a fibrous adsorbent excellent in the ability to adsorb environmental pollutants such as dioxins, heat resistance and chemical resistance, and a filter composed of the adsorbent are provided.
本発明のアルミナ質繊維は、アルミナ成分が６０〜１００質量％、シリカ成分が０〜４０質量％の化学組成を有し、比表面積が１０〜２５０ｍ２／ｇ、好ましくは３０〜２００ｍ２／ｇである。耐熱性・耐薬品性の点からはアルミナ成分が多いほどよいが、アルミナ成分を多くすると繊維が脆くなり、また生産性も低下する恐れがあるので、アルミナ成分が８０〜９５質量％、シリカ成分が５〜２０質量％であることが好ましい。また、上記比表面積の範囲において、触媒担体、吸着材、吸着フィルターとして十分な機能を発現し、しかも繊維強度も十分なものとなる。 The alumina fiber of the present invention has a chemical composition in which the alumina component is 60 to 100% by mass and the silica component is 0 to 40% by mass, and the specific surface area is 10 to 250 m 2 / g, preferably 30 to 200 m 2 / g. It is. From the standpoint of heat resistance and chemical resistance, the more the alumina component, the better. However, if the alumina component is increased, the fiber becomes brittle and the productivity may be lowered. Therefore, the alumina component is 80 to 95% by mass, the silica component. Is preferably 5 to 20% by mass. Moreover, within the range of the specific surface area, sufficient functions as a catalyst carrier, an adsorbent, and an adsorption filter are exhibited, and the fiber strength is sufficient.
本発明のアルミナ質繊維は、少なくとも繊維表面がスピネル型結晶で変質されているものであり、特に繊維表面と共に繊維内部までがこのようなスピネル型結晶で変質されているものが好ましい。ここで、スピネル型結晶とは、アルミナ質のスピネル型結晶として、例えばγ−アルミナ，δ−アルミナ，θ−アルミナ等の中間アルミナ等であり、アルミナシリカ質のスピネル型結晶として、例えばＡｌ−Ｓｉスピネル等である。また、変質とは、少なくとも繊維表面がこれらの結晶となっていることであるが、特にγ−アルミナ又はＡｌ−Ｓｉスピネルの少なくとも一方によって繊維表面全部が覆われていることが好ましい。変質が不十分であると、繊維表面が細かい微粒子結晶で覆われる割合が少なくなり、比表面積１０〜２５０ｍ２／ｇの実現が難しくなる。変質は、繊維表面の結晶構造を透過型電子顕微鏡（ＴＥＭ）観察によって確認することができ、Ｘ線回折分析と併用すればより確実となる。 The alumina fiber of the present invention is one in which at least the fiber surface is modified with spinel crystals, and in particular, the fiber surface and the inside of the fiber are modified with such spinel crystals. Here, the spinel crystal is an alumina spinel crystal, for example, intermediate alumina such as γ-alumina, δ-alumina, θ-alumina, etc., and an alumina siliceous spinel crystal is, for example, Al-Si. Spinel etc. The alteration means that at least the fiber surface is made of these crystals, and it is particularly preferable that the entire fiber surface is covered with at least one of γ-alumina or Al—Si spinel. If the alteration is insufficient, the ratio of the fiber surface covered with fine particulate crystals decreases, and it becomes difficult to achieve a specific surface area of 10 to 250 m 2 / g. The alteration can be confirmed by observing the crystal structure of the fiber surface with a transmission electron microscope (TEM), and becomes more reliable when used in combination with X-ray diffraction analysis.
本発明のアルミナ質繊維の製造方法は、本発明のアルミナ質繊維の製造に適用できる。本発明で用いられる紡糸原液は、アルミナ源としてオキシ塩化アルミニウム、シリカ源としてコロイダルシリカ、紡糸助剤としてポリビニルアルコール、ポリエチレンオキサイド及びポリエチレングリコールから選ばれた少なくとも一種を用いて調製され、それらの割合は、アルミナ成分とシリカ成分の合計１００質量部に対してアルミナ分を６０質量部以上（１００を含む）、シリカ分を４０質量部以下（０を含む）、紡糸助剤を３〜１８質量部とする。ポリビニルアルコールは、部分ケン化物、完全ケン化物のいずれか、又はその両方であってもよい。 The method for producing alumina fibers of the present invention can be applied to the production of alumina fibers of the present invention. The spinning dope used in the present invention is prepared using at least one selected from aluminum oxychloride as an alumina source, colloidal silica as a silica source, polyvinyl alcohol, polyethylene oxide and polyethylene glycol as a spinning aid, and the ratio thereof is as follows. The alumina content is 60 parts by mass or more (including 100), the silica content is 40 parts by mass or less (including 0), and the spinning aid is 3 to 18 parts by mass with respect to a total of 100 parts by mass of the alumina component and the silica component. To do. The polyvinyl alcohol may be a partially saponified product, a fully saponified product, or both.
オキシ塩化アルミニウムとコロイダルシリカの配合量を、アルミナ成分とシリカ成分の合計１００質量部に対してアルミナ分を６０質量部以上、シリカ分を４０質量部以下とするのは、アルミナ成分６０〜１００質量％、シリカ成分０〜４０質量％のアルミナ質繊維を製造するのに必要であるからである。紡糸助剤の使用量が上記範囲を逸脱すると、紡糸時の液糸の延伸が十分でなくなり、繊維が切れるか、ショットと呼ばれる未繊維化物の生成が多くなるか、繊維径が太くなりすぎるなどの恐れがある。特に好ましい紡糸助剤の使用量は、紡糸原液中の上記アルミナ分とシリカ分の合計１００質量部に対して４〜９質量部である。 The amount of alumina oxychloride and colloidal silica is 60 parts by mass or more and 40 parts by mass or less of the alumina component with respect to 100 parts by mass of the total of the alumina component and the silica component. This is because it is necessary to produce an alumina fiber having a silica component of 0 to 40% by mass. If the amount of the spinning aid deviates from the above range, the drawing of the liquid yarn at the time of spinning becomes insufficient, the fiber breaks, the production of unfibrinated products called shots increases, or the fiber diameter becomes too thick. There is a fear. A particularly preferable amount of the spinning aid is 4 to 9 parts by mass with respect to a total of 100 parts by mass of the alumina component and the silica component in the spinning dope.
紡糸原液の粘度は、５００〜２００００ｍＰａ・ｓ、特に１０００〜５０００ｍＰａ・ｓであることが好ましい。粘度がこれよりも著しく小さいと繊維化（紡糸）が困難となる恐れがあり、また著しく大きいと、繊維径が大きくなりすぎ、脆い繊維となりやすくなる。紡糸原液の繊維化（紡糸）は、例えば遠心法、押し出し法、吹き出し法等の各種の紡糸法で行うことができる。 The viscosity of the spinning dope is preferably 500 to 20000 mPa · s, more preferably 1000 to 5000 mPa · s. If the viscosity is significantly smaller than this, fiberization (spinning) may be difficult. If the viscosity is extremely large, the fiber diameter becomes too large and brittle fibers tend to be formed. The spinning solution can be made into fibers (spun) by various spinning methods such as a centrifugal method, an extrusion method, and a blowing method.
本発明で重要なことは、スピネル型結晶で変質させるための紡糸後の焼成条件であり、毎分２〜５０℃の速度で７００〜１１５０℃まで昇温し、この温度で保持することである。好ましくは、毎分５〜３０℃の速度で８５０〜１０００℃まで昇温し、この温度範囲の保持時間を１５〜９０分とすることである。保持温度が７００℃未満では、スピネル型結晶の生成が不十分となり、１１５０℃をこえると、一旦生成したスピネル型結晶が相転移し、ムライト、α−アルミナ等の高温安定相に移行するので、結晶粒径が増大し、比表面積が小さくなり、しかも脆い繊維となる。 What is important in the present invention is post-spinning firing conditions for transformation with spinel crystals, and the temperature is raised to 700-1150 ° C. at a rate of 2-50 ° C. per minute and maintained at this temperature. . Preferably, the temperature is raised to 850 to 1000 ° C. at a rate of 5 to 30 ° C. per minute, and the holding time in this temperature range is 15 to 90 minutes. If the holding temperature is less than 700 ° C., the generation of spinel crystals is insufficient. The crystal grain size increases, the specific surface area decreases, and the fiber becomes brittle.
一般に、紡糸した繊維から水分、塩素分、有機分が脱離すると繊維の強度は低下し、形状は崩れやすい状態となるが、本発明において紡糸後の昇温速度が２℃／分未満では、形状が崩れやすい状態での滞留時間が長すぎるため、粉化した繊維となりやすくなり、しかも生産性が低下する。一方、昇温速度が５０℃／分をこえると繊維内部の温度が十分あがらないうちに高温域に達してしまい、この高温域で急激に水分、塩素分、有機分の脱離が起こるので繊維に大きな空隙ができやすくなり、強度の低い繊維となる恐れがあること、更には塩化水素ガスの脱離、紡糸助剤の燃焼分解不良によって、最終製品に塩素分や有機分が残存する恐れもある。 In general, when moisture, chlorine, and organic components are desorbed from the spun fiber, the strength of the fiber decreases and the shape tends to collapse. However, in the present invention, if the heating rate after spinning is less than 2 ° C./min, Since the residence time in a state where the shape tends to collapse is too long, it becomes easy to become a pulverized fiber, and the productivity is lowered. On the other hand, if the rate of temperature rise exceeds 50 ° C./min, the fiber will reach a high temperature range before the temperature rises sufficiently, and the moisture, chlorine content, and organic content will be rapidly desorbed at this high temperature range. Large voids can easily be formed, resulting in low-strength fibers. In addition, chlorine and organic components may remain in the final product due to desorption of hydrogen chloride gas and poor combustion decomposition of the spinning aid. is there.
本発明のアルミナ質繊維は、そのまま繊維状触媒担体又は繊維状吸着材として使用することができるし、更には繊維状吸着材を成形加工した吸着フィルターとして使用することができる。成形加工は、例えばアルミナ質繊維を水に分散させ、成形用の有機バインダー、高温での保形用の無機バインダー及び凝集剤等の少なくとも一方を添加し、抄造成形法等によってフェルト状の成形体とすることによって行うことができる。繊維状触媒担体は、例えばメタンの低温燃焼用触媒の担体等として用いることができ、また繊維状吸着材及び吸着フィルターは、例えばダイオキシン類を含む排出ガスの処理用として、各種焼却炉の排ガス処理設備や除外設備用のフィルター等として用いることができる。 The alumina fiber of the present invention can be used as it is as a fibrous catalyst carrier or a fibrous adsorbent, and further can be used as an adsorption filter obtained by molding the fibrous adsorbent. The molding process is performed by, for example, dispersing an alumina fiber in water, adding at least one of an organic binder for molding, an inorganic binder for shape retention at high temperature, a flocculant, and the like, and forming a felt-like molded body by a papermaking molding method or the like. It can be done by. The fibrous catalyst carrier can be used, for example, as a carrier for a catalyst for low-temperature combustion of methane, and the fibrous adsorbent and the adsorption filter are, for example, for exhaust gas treatment of various incinerators for treating exhaust gas containing dioxins. It can be used as a filter for equipment or excluded equipment.
実施例１
アルミナ固形分濃度で２２質量％のオキシ塩化アルミニウム水溶液４５５０ｇ（アルミナ分として１００１ｇ）と、シリカ濃度２０質量％のコロイダルシリカ１２５０ｇ（シリカ分として２５０ｇ）と、部分ケン化ポリビニルアルコールの１０質量％水溶液６００ｇ（紡糸原液中のアルミナ分とシリカ分の合計１００質量部に対して部分ケン化ポリビニルアルコールが４．８質量部）とを混合した後、減圧脱水濃縮を行い、粘度３０００ｍＰａ・ｓの紡糸原液を調製した。これを、円周面に直径０．５ｍｍの孔を３００個設けられた直径１００ｍｍの中空円盤を回転させながらこれらの孔から飛び出させて繊維化すると同時に、５００℃の熱風により乾燥固化させて繊維前駆体を製造した。その後、繊維前駆体を、速度８℃／分で最高温度９００℃まで昇温し、この温度で４０分間保持する焼成を行ってアルミナ質繊維を製造した。
Example 1
4550 g of aluminum oxychloride aqueous solution having a solid alumina concentration of 22% by mass (1001 g as an alumina component), 1250 g of colloidal silica having a silica concentration of 20% by mass (250 g as a silica component), and 600 g of a 10% by mass aqueous solution of partially saponified polyvinyl alcohol. (The partially saponified polyvinyl alcohol is 4.8 parts by mass with respect to a total of 100 parts by mass of alumina and silica in the spinning undiluted solution), followed by vacuum dehydration and concentration to obtain a spinning undiluted solution having a viscosity of 3000 mPa · s. Prepared. The fiber is made to fly out of these holes by spinning a hollow disk with a diameter of 100 mm having 300 holes with a diameter of 0.5 mm on the circumferential surface, and simultaneously dried and solidified with hot air at 500 ° C. A precursor was produced. Thereafter, the fiber precursor was heated to a maximum temperature of 900 ° C. at a rate of 8 ° C./min, and calcination was carried out at this temperature for 40 minutes to produce alumina fibers.
得られたアルミナ質繊維は、アルミナ成分が８０質量％、シリカ成分が２０質量％であり、平均繊維径が３．５μｍ、ＢＥＴ法比表面積が１７０ｍ２／ｇであった。このアルミナ質繊維を樹脂に埋め込み、これを削って繊維の表面部のみを露出させ、透過型電子顕微鏡（ＴＥＭ）観察を行ったところ、結晶生成が認められた。また、粉末Ｘ線回折法にて結晶状態を測定したところ、スピネル型結晶の回折ピークのみが検出された。 The obtained alumina fiber had an alumina component of 80% by mass and a silica component of 20% by mass, an average fiber diameter of 3.5 μm, and a BET specific surface area of 170 m 2 / g. When this alumina fiber was embedded in a resin, it was shaved to expose only the surface portion of the fiber, and observation with a transmission electron microscope (TEM) revealed that crystal formation was observed. Further, when the crystal state was measured by the powder X-ray diffraction method, only the diffraction peak of the spinel crystal was detected.
つぎに、繊維状触媒担体、繊維状吸着材又はフィルターの用途として適合しているかどうかを評価するため、風速に対する耐久性試験として、３０ｍｍ×３０ｍｍ×３０ｍｍの繊維の積層体マット、及び抄造成形法によって製作した繊維質成形体を用意し、その一面に対して、５ｍｍ離れた位置から、ノズル（直径５ｍｍ）を用い、２０ｍ／秒の空気を５秒間噴射、５秒間停止する操作を３時間繰り返して行い、試験前後の繊維積層体の質量変化率を測定した。その結果、質量減量率は積層体マットで０．３％、繊維質成形体で０．４％であった。 Next, in order to evaluate whether it is suitable for use as a fibrous catalyst carrier, fibrous adsorbent or filter, as a durability test against wind speed, a laminated mat of 30 mm × 30 mm × 30 mm fibers, and a papermaking molding method Prepare the fiber molded body manufactured by the above, and use a nozzle (diameter 5 mm) from a position 5 mm away from one side, spray 20 m / second of air for 5 seconds, and repeat the operation of stopping for 5 seconds for 3 hours. The mass change rate of the fiber laminate before and after the test was measured. As a result, the weight loss rate was 0.3% for the laminated mat and 0.4% for the fibrous molded body.
以上のことから、本実施例で製造されたアルミナ質繊維は、アルミナ成分が８０質量％、シリカ成分が２０質量％の化学組成を有していることから耐熱性・耐薬品性に優れ、またＢＥＴ法比表面積が１７０ｍ２／ｇで、その少なくとも表面がスピネル型結晶で変質されていることから十分な触媒担持能力ないしは環境汚染物質の吸着能力を有し、しかも繊維の強度が高いため風速に対する耐久性が高くなり、繊維状触媒担体、繊維状吸着材又はフィルターの用途として適合していることがわかった。 From the above, the alumina fiber produced in this example has a chemical composition having an alumina component of 80% by mass and a silica component of 20% by mass, and thus has excellent heat resistance and chemical resistance. The BET method specific surface area is 170 m 2 / g, and at least the surface is modified by spinel crystals, so that it has sufficient catalyst carrying capacity or adsorption capacity for environmental pollutants, and the fiber strength is high, so It has been found that the durability is high and it is suitable for use as a fibrous catalyst support, a fibrous adsorbent or a filter.
実施例２
コロイダルシリカの使用量を３３３０ｇ（シリカ分として６６６ｇ）としたこと以外は、実施例１と同様の方法でアルミナ質繊維を製造し、評価した。
Example 2
Alumina fibers were produced and evaluated in the same manner as in Example 1 except that the amount of colloidal silica used was 3330 g (666 g as the silica content).
実施例３
コロイダルシリカを配合しなかったこと以外は、実施例１と同様の方法でアルミナ質繊維を製造し、評価した。
Example 3
Alumina fibers were produced and evaluated in the same manner as in Example 1 except that no colloidal silica was added.
実施例４
焼成の最高温度を７００℃とし、この温度で１５分間保持する焼成をしたこと以外は、実施例１と同様の方法でアルミナ質繊維を製造し、評価した。
Example 4
Aluminous fibers were produced and evaluated in the same manner as in Example 1 except that the maximum firing temperature was 700 ° C. and firing was performed at this temperature for 15 minutes.
実施例５
焼成時の最高温度を１１５０℃とし、この温度で９０分間保持する焼成をしたこと以外は、実施例１と同様の方法でアルミナ質繊維を製造し、評価した。
Example 5
Aluminous fibers were produced and evaluated in the same manner as in Example 1 except that the maximum temperature during firing was 1150 ° C. and firing was performed at this temperature for 90 minutes.
実施例６
１０質量％部分ケン化ポリビニルアルコール水溶液の使用量を３７５ｇ（紡糸原液中のアルミナ分とシリカ分の合計１００質量部に対して３質量部）としたこと以外は、実施例１と同様の方法でアルミナ質繊維を製造し、評価した。
Example 6
The same method as in Example 1 except that the amount of the 10% by mass partially saponified polyvinyl alcohol aqueous solution was 375 g (3 parts by mass with respect to 100 parts by mass in total of alumina and silica in the spinning dope). Alumina fibers were manufactured and evaluated.
実施例７
１０質量％部分ケン化ポリビニルアルコール水溶液の使用量を２２５０ｇ（紡糸原液中のアルミナ分とシリカ分の合計１００質量部に対して１８質量部）としたこと以外は、実施例１と同様の方法でアルミナ質繊維を製造し、評価した。
Example 7
The same method as in Example 1 except that the amount of 10% by mass partially saponified polyvinyl alcohol aqueous solution was 2250 g (18 parts by mass with respect to 100 parts by mass in total of alumina and silica in the spinning dope). Alumina fibers were manufactured and evaluated.
実施例８
部分ケン化ポリビニルアルコールの代わりに完全ケン化ポリビニルアルコールを用いたこと以外は、実施例１と同様の方法でアルミナ質繊維を製造し、評価した。
Example 8
Aluminous fibers were produced and evaluated in the same manner as in Example 1 except that completely saponified polyvinyl alcohol was used instead of partially saponified polyvinyl alcohol.
実施例９
部分ケン化ポリビニルアルコールの代わりにポリエチレンオキサイドを用いたこと以外は、実施例１と同様の方法でアルミナ質繊維を製造し、評価した。
Example 9
Alumina fibers were produced and evaluated in the same manner as in Example 1 except that polyethylene oxide was used instead of partially saponified polyvinyl alcohol.
実施例１０
部分ケン化ポリビニルアルコールの代わりにポリエチレングリコールを用いたこと以外は、実施例１と同様の方法でアルミナ質繊維を製造し、評価した。
Example 10
Alumina fibers were produced and evaluated in the same manner as in Example 1 except that polyethylene glycol was used instead of partially saponified polyvinyl alcohol.
実施例１１
焼成時の昇温速度を毎分２℃としたこと以外は、実施例１と同様の方法でアルミナ質繊維を製造し、評価した。
Example 11
Alumina fibers were produced and evaluated in the same manner as in Example 1 except that the temperature rising rate during firing was 2 ° C. per minute.
実施例１２
焼成時の昇温速度を毎分５０℃としたこと以外は、実施例１と同様の方法でアルミナ質繊維を製造し、評価した。
Example 12
Alumina fibers were produced and evaluated in the same manner as in Example 1 except that the temperature rising rate during firing was 50 ° C. per minute.
比較例１
配合するコロイダルシリカの質量を５０００ｇ（シリカ分として１０００ｇ）としたこと以外は、実施例１と同様の方法でアルミナ質繊維を製造し、評価した。
Comparative Example 1
Aluminous fibers were produced and evaluated in the same manner as in Example 1 except that the mass of the colloidal silica to be blended was 5000 g (1000 g as the silica content).
比較例２
焼成時の最高温度を１２５０℃としたこと以外は、実施例１と同様の方法でアルミナ質繊維を製造し、評価した。
Comparative Example 2
Alumina fibers were produced and evaluated in the same manner as in Example 1 except that the maximum temperature during firing was 1250 ° C.
以上の結果を表１に示す。表1から、比較例１は、実施例に比べて比表面積が小さく、触媒担体、吸着材、フィルターとしては適切ではなかった。これは、紡糸原液のシリカ成分を多くしすぎるとガラスが繊維表面を覆ってしまったためと推定される。また、比較例２の繊維は、比表面積が小さく、風速に対する耐久性も劣り、しかもスピネル型結晶のＸ線回折ピーク以外にムライトのピークが検出された。これは、焼成の最高温度を高くしすぎると、繊維の表面等にムライト、α−アルミナ等の粒径の大きい結晶が生成したためと推定される。 The results are shown in Table 1. From Table 1, the comparative example 1 had a small specific surface area compared with the Example, and was not suitable as a catalyst support | carrier, an adsorbent, and a filter. This is presumably because the glass covered the fiber surface when the silica component of the spinning dope was increased too much. Further, the fiber of Comparative Example 2 had a small specific surface area, poor durability against wind speed, and a mullite peak was detected in addition to the X-ray diffraction peak of the spinel crystal. This is presumably because, when the maximum firing temperature was too high, crystals having a large particle size such as mullite and α-alumina were formed on the fiber surface and the like.
本発明のアルミナ質繊維は比表面積が大きいことから金属等の他物質の濡れ性が高いと考えられ、他物質との複合化に有利である。また、高強度で十分な耐熱性を有した繊維であるため、繊維状触媒担体、繊維状吸着材及びフィルターは勿論のこと、これら以外に、繊維強化金属、繊維強化プラスチック等の各種複合材料の強化用繊維として使用できる。また、本発明の繊維状触媒担体は、例えばメタンの低温燃焼用触媒の担体等として用いることができ、また繊維状吸着材及び吸着フィルターは、例えばダイオキシン類を含む排出ガスの処理用として、各種焼却炉の排ガス処理設備や除外設備用のフィルター等として用いることができる。 Since the alumina fiber of the present invention has a large specific surface area, it is considered that the wettability of other substances such as metals is high, which is advantageous for compounding with other substances. In addition, since the fiber has high strength and sufficient heat resistance, not only the fibrous catalyst carrier, fibrous adsorbent and filter, but also various composite materials such as fiber reinforced metal and fiber reinforced plastic can be used. Can be used as a reinforcing fiber. The fibrous catalyst carrier of the present invention can be used, for example, as a carrier for a low-temperature combustion catalyst for methane, and the fibrous adsorbent and the adsorption filter can be used for various kinds of exhaust gas treatment including, for example, dioxins. It can be used as a filter for an exhaust gas treatment facility of an incinerator or an exclusion facility.
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| WO2013114808A1 (en) * | 2012-01-31 | 2013-08-08 | ニチアス株式会社 | Inorganic fiber and process for manufacturing same |
| WO2014069589A1 (en) * | 2012-10-31 | 2014-05-08 | 電気化学工業株式会社 | Alumina-based fibrous mass, process for producing same, and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007244950A (en) * | 2006-03-14 | 2007-09-27 | Nissan Motor Co Ltd | Particulate filter type exhaust gas cleaning catalyst and particulate filter |
| WO2013114808A1 (en) * | 2012-01-31 | 2013-08-08 | ニチアス株式会社 | Inorganic fiber and process for manufacturing same |
| JPWO2013114808A1 (en) * | 2012-01-31 | 2015-05-11 | ニチアス株式会社 | Inorganic fiber and method for producing the same |
| US9302947B2 (en) | 2012-01-31 | 2016-04-05 | Nichias Corporation | Inorganic fiber and process for manufacturing same |
| WO2014069589A1 (en) * | 2012-10-31 | 2014-05-08 | 電気化学工業株式会社 | Alumina-based fibrous mass, process for producing same, and use |
| CN104884690A (en) * | 2012-10-31 | 2015-09-02 | 电气化学工业株式会社 | Alumina-based fibrous mass, process for producing same, and use |
| JPWO2014069589A1 (en) * | 2012-10-31 | 2016-09-08 | デンカ株式会社 | Alumina fiber assembly, its production method and use |
| US9827553B2 (en) | 2012-10-31 | 2017-11-28 | Denka Company Limited | Alumina-based fibrous mass, process for producing same, and use |
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