JP3228983B2 - Catalytic fiber - Google Patents
Catalytic fiberInfo
- Publication number
- JP3228983B2 JP3228983B2 JP00647292A JP647292A JP3228983B2 JP 3228983 B2 JP3228983 B2 JP 3228983B2 JP 00647292 A JP00647292 A JP 00647292A JP 647292 A JP647292 A JP 647292A JP 3228983 B2 JP3228983 B2 JP 3228983B2
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- catalyst
- alkoxide
- anatase
- titanium oxide
- 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.)
- Expired - Fee Related
Links
- 239000000835 fiber Substances 0.000 title claims description 56
- 230000003197 catalytic effect Effects 0.000 title description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 37
- 239000003054 catalyst Substances 0.000 claims description 31
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 21
- -1 Titanium alkoxide Chemical class 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 12
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 9
- 150000004703 alkoxides Chemical class 0.000 claims description 9
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 3
- 150000001875 compounds Chemical class 0.000 claims 2
- 240000006670 Chlorogalum pomeridianum Species 0.000 claims 1
- 235000007836 Chlorogalum pomeridianum Nutrition 0.000 claims 1
- 239000009895 amole Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 239000000428 dust Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 150000003682 vanadium compounds Chemical class 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002513 implantation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 125000005287 vanadyl group Chemical group 0.000 description 4
- 238000009941 weaving Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- CRNJBCMSTRNIOX-UHFFFAOYSA-N methanolate silicon(4+) Chemical compound [Si+4].[O-]C.[O-]C.[O-]C.[O-]C CRNJBCMSTRNIOX-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 241000212978 Amorpha <angiosperm> Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical group [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】本発明は都市ごみ焼却炉，下水汚
染焼却炉，産業廃棄物焼却炉，ボイラおよびディーゼル
エンジンなどの排ガス処理装置に使用する触媒フィルタ
の構造材料に有用な触媒繊維に関し、本発明の触媒繊維
を使用した触媒フィルタは排ガス中の窒素酸化物やばい
じん，さらにはフッ素，フッ化水素，塩素，塩化水素，
硫黄酸化物などの酸性ガスを処理するのに適する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalytic fiber useful as a structural material for a catalytic filter used in an exhaust gas treatment device such as a municipal solid waste incinerator, a sewage pollution incinerator, an industrial waste incinerator, a boiler and a diesel engine. The catalyst filter using the catalyst fiber of the present invention can be used for nitrogen oxides and dust in exhaust gas, as well as fluorine, hydrogen fluoride, chlorine, hydrogen chloride,
Suitable for treating acidic gases such as sulfur oxides.
【０００２】[0002]
【従来の技術】従来、排ガス中のばいじんを除去するた
めには、電気集塵機（ＥＰ）やサイクロン，ベンチュリ
ークラバ，バグフィルタなどが使用されている。また、
排ガス中の窒素酸化物を除去するためにはアンモニアを
還元剤とする選択的触媒法があり、触媒はハニカム状ま
たはペレット状のものが使用されている。通常、燃焼排
ガスには窒素酸化物とばいじんを含んでおり、両者を除
去するためには集塵装置と脱硝装置を併設する必要があ
る。また、バグフィルタには通常ＥガラスあるいはＳガ
ラスの繊維が使用されている。2. Description of the Related Art Conventionally, an electric dust collector (EP), a cyclone, a venturi clubber, a bag filter and the like have been used to remove soot and dust in exhaust gas. Also,
In order to remove nitrogen oxides in exhaust gas, there is a selective catalytic method using ammonia as a reducing agent, and a honeycomb-shaped or pellet-shaped catalyst is used. Normally, the combustion exhaust gas contains nitrogen oxides and dust, and in order to remove both, it is necessary to provide a dust collector and a denitration device together. Further, a fiber of E glass or S glass is usually used for the bag filter.
【０００３】[0003]
【発明が解決しようとする課題】本発明は脱硝と除塵さ
らには酸性ガスの除去を一つの処理装置で処理すること
を可能とする触媒フィルタの構造材となる触媒繊維を提
供しようとするものである。SUMMARY OF THE INVENTION The present invention is to provide a catalyst fiber which is a structural material of a catalyst filter which can perform denitration, dust removal, and removal of an acid gas by one processing apparatus. is there.
【０００４】[0004]
【課題を解決するための手段】本発明は次の（１）〜
（３）の構成を有する触媒繊維である。 （１）チタンアルコキシドおよびバナジウム化合物、あ
るいはチタンアルコキシドおよびバナジウム化合物と他
のアルコキシドとの混合アルコキシド溶液を加水分解し
ゲル化させるゾルゲル法により作製したアモルファス繊
維を熱処理し、アナターゼ型酸化チタンと酸化バナジウ
ムの結晶を析出させることによって得られるアモルファ
ス酸化チタン相とアナターゼ型酸化チタン相が共存し、
かつ酸化バナジウムを含む繊維であることを特徴とする
触媒繊維。Means for Solving the Problems The present invention provides the following (1)-
A catalyst fiber having the configuration of (3). (1) titanium alkoxide and vanadium compound,
Or titanium alkoxide and vanadium compounds and others
Of the mixed alkoxide solution with the alkoxide of
Amorphous fiber produced by sol-gel method for gelation
Heat-treated the fibers, anatase-type titanium oxide and vanadium oxide
Amorpha obtained by depositing crystal of crystals
Titanium oxide phase and anatase type titanium oxide phase coexist,
The catalyst fiber characterized by and a fiber comprising a vanadium oxide.
【０００５】（２）酸化チタンの含有率が２０〜９５ｗ
ｔ％であり、かつ酸化バナジウムの含有率が１〜５ｗｔ
％であることを特徴とする上記（１）記載の触媒繊維。(2) The content of titanium oxide is 20 to 95 watts
t%, and the content of vanadium oxide is 1 to 5 wt.
% Of the catalyst fiber according to the above (1).
【０００６】（３）アナターゼの結晶化率が１０％以上
であることを特徴とする上記（１）又は（２）記載の触
媒繊維。 (3) The catalyst fiber according to the above (1) or (2), wherein the crystallization ratio of anatase is 10% or more .
【０００７】本発明の触媒繊維はチタンアルコキシドお
よびバナジウム化合物、あるいはチタンアルコキシドお
よびバナジウム化合物と他のアルコキシドとの混合アル
コキシド溶液を加水分解しゲル化させるゾルゲル法によ
り作製したアモルファス繊維を熱処理し、アナターゼ型
酸化チタンと酸化バナジウムの結晶を析出させることに
よって得られる。The catalyst fiber of the present invention is obtained by subjecting an amorphous fiber produced by a sol-gel method of hydrolyzing and gelling a titanium alkoxide and a vanadium compound or a mixed alkoxide solution of a titanium alkoxide and a vanadium compound and another alkoxide to an anatase type. It is obtained by depositing crystals of titanium oxide and vanadium oxide.
【０００８】チタンアルコキシドはチタンエトキシド，
チタンプロポキシド、チタンブトキシド等が利用できる
が、汎用性からチタンイソプロポキシドが好ましい。ま
た、バナジウム化合物は溶媒として用いるアルコールに
可溶なものであればよく、例えばバナジルアルコキシド
や塩化バナジルなどを用いることができる。[0008] Titanium alkoxide is titanium ethoxide,
Titanium propoxide, titanium butoxide and the like can be used, but titanium isopropoxide is preferable from the viewpoint of versatility. Further, the vanadium compound only needs to be soluble in alcohol used as a solvent, and for example, vanadyl alkoxide, vanadyl chloride and the like can be used.
【０００９】また、複合アルコキシドを作製する場合は
アモルファス繊維の骨格材料となりやすい酸化物のアル
コキシド、例えばシリコンアルコキシド，アルミニウム
アルコキシド，ボロンアルコキシド等が利用できるが、
汎用性からシリコンアルコキシドなかでもシリコンメト
キシドかシリコンエトキシドが好ましい。In the case of producing a composite alkoxide, an oxide alkoxide which is likely to be a skeleton material of an amorphous fiber, for example, silicon alkoxide, aluminum alkoxide, boron alkoxide and the like can be used.
Of the silicon alkoxides, silicon methoxide or silicon ethoxide is preferred from the viewpoint of versatility.
【００１０】上記アルコキシド溶液を加水分解しアモル
ファス繊維を紡糸した後熱処理しアナターゼ型酸化チタ
ンと酸化バナジウムの結晶を析出させる。熱処理温度は
結晶化の遅いアナターゼ結晶が析出する温度、すなわち
２００〜７００℃の範囲、中でも３５０℃〜５５０℃で
熱処理することが好ましい。The alkoxide solution is hydrolyzed to spin an amorphous fiber, and then heat-treated to precipitate crystals of anatase-type titanium oxide and vanadium oxide. The heat treatment is preferably performed at a temperature at which anatase crystals having a low crystallization rate are precipitated, that is, in the range of 200 to 700 ° C, and particularly at 350 to 550 ° C.
【００１１】アモルファス繊維を熱処理してアナターゼ
型結晶を析出させる場合の結晶化率は１０〜９０％中で
も３０〜５０％結晶化させた繊維が好ましい。When the amorphous fiber is heat-treated to precipitate anatase-type crystals, the crystallization ratio is preferably from 10 to 90%, and more preferably from 30 to 50%.
【００１２】繊維中の触媒含有率は大きいほど好まし
い。しかしアモルファス繊維の製造の容易さを考慮する
場合は、酸化珪素や酸化アルミニウムのようなガラス網
目形成材料を加えることができる。しかし触媒機能を考
慮すると触媒含有率の最小率として１０％は必要であ
る。The higher the catalyst content in the fiber, the better. However, when considering the easiness of producing the amorphous fiber, a glass network forming material such as silicon oxide or aluminum oxide can be added. However, considering the catalytic function, 10% is required as the minimum rate of the catalyst content.
【００１３】また触媒活性の点から、酸化チタンと酸化
バナジウムの比率は重量比で９５：５〜８０：１０程度
が好ましい。From the viewpoint of catalytic activity, the ratio of titanium oxide to vanadium oxide is preferably about 95: 5 to 80:10 by weight.
【００１４】[0014]
【作用】本発明の触媒繊維は脱硝に有効なアナターゼ型
酸化チタンと酸化バナジウムが析出しており、この繊維
を使用してフィルタを形成すると触媒機能と除塵機能を
有する触媒フィルタが得られる。触媒は長時間使用する
と様々な要因により活性が低下し脱硝率が低下する。し
かし本発明の触媒繊維はアモルファス繊維を熱処理し結
晶を析出させる方法のため、触媒繊維にはアモルファス
酸化チタン相とアナターゼ型酸化チタン相が共存してお
り、使用中の熱エネルギによりアモルファス酸化チタン
相が徐々にアナターゼ型酸化チタンに転移するため、触
媒成分であるアナターゼ型酸化チタンが被毒されても新
たなアナターゼ結晶が析出する。そのため脱硝率が触媒
の被毒によって低下することはない。The catalytic fiber of the present invention has anatase-type titanium oxide and vanadium oxide which are effective for denitration, and when a filter is formed using this fiber, a catalytic filter having a catalytic function and a dust removing function can be obtained. When the catalyst is used for a long time, the activity is reduced due to various factors and the denitration rate is reduced. However, since the catalyst fiber of the present invention is a method of precipitating crystals by heat treatment of the amorphous fiber , an amorphous titanium oxide phase and an anatase-type titanium oxide phase coexist in the catalyst fiber. Gradually transitions to anatase-type titanium oxide, so that even if the anatase-type titanium oxide as a catalyst component is poisoned, new anatase crystals are precipitated. Therefore, the denitration rate does not decrease due to the poisoning of the catalyst.
【００１５】また、アモルファス繊維の引張強度や折曲
強度は一般のガラス繊維のそれらに近く大きい値を示
す。しかし十分に熱処理をしてアモルファス繊維を全て
結晶に転移させると多結晶体の繊維になり、結晶の粒界
に起因して繊維の強度が低下する。そのためアモルファ
ス繊維を熱処理してアナターゼを析出させる場合は、一
部結晶化させてアモルファスとアナターゼを共存させる
必要がある。Further, the tensile strength and bending strength of the amorphous fiber show large values close to those of the general glass fiber. However, when heat treatment is sufficiently performed to convert all of the amorphous fibers into crystals, the fibers become polycrystalline fibers, and the strength of the fibers decreases due to crystal grain boundaries. Therefore, when an anatase is deposited by heat-treating an amorphous fiber, it is necessary to partially crystallize the anatase to allow the amorphous and anatase to coexist.
【００１６】[0016]
（実施例１）まず、市販のシリコンメトキシド１２６ｇ
に、ＨＣｌを０．３ｇおよびＨ2 Ｏを２２ｇおよびエタ
ノール１２６ｇを混合した液を攪拌しながら滴下混合し
た後、８０℃で２時間攪拌を続けた。２時間経過後チタ
ンイソプロポキシド：１６８ｇを加えてさらに２時間加
熱攪拌した後、この溶液を０℃に冷却し、Ｈ2 Ｏ：１６
ｇおよびエタノール：１６８ｇからなる混合液を攪拌し
ながら混合した。これを再び８０℃で２時間攪拌し、バ
ナジルテトラｎ−プロポキシド：６．８ｇを混合して、
さらに８０℃で２時間攪拌した後、減圧濃縮してアルコ
ールを除去して紡糸可能な粘稠液を調製した。(Example 1) First, 126 g of commercially available silicon methoxide
Then, a solution obtained by mixing 0.3 g of HCl, 22 g of H 2 O, and 126 g of ethanol was added dropwise while stirring, and then stirring was continued at 80 ° C. for 2 hours. After 2 hours, 168 g of titanium isopropoxide was added, and the mixture was further heated and stirred for 2 hours. Then, the solution was cooled to 0 ° C., and H 2 O: 16
g and ethanol: 168 g were mixed with stirring. This was again stirred at 80 ° C. for 2 hours, and vanadyl tetra n-propoxide: 6.8 g was mixed.
After stirring at 80 ° C. for 2 hours, the mixture was concentrated under reduced pressure to remove the alcohol to prepare a viscous liquid capable of spinning.
【００１７】この粘稠液から繊維を紡糸し、ＳｉＯ2 ：
ＴｉＯ2 ：Ｖ2 Ｏ5 ＝５０：４７．５：２．５（ｗｔ）
のアモルファス繊維を作製した。このアモルファス繊維
を５００℃で２時間熱処理しアナターゼ型酸化チタンを
１０％含む触媒繊維を作製した。A fiber is spun from this viscous liquid, and SiO 2 :
TiO 2 : V 2 O 5 = 50: 47.5: 2.5 (wt)
Was produced. This amorphous fiber was heat-treated at 500 ° C. for 2 hours to prepare a catalyst fiber containing 10% of anatase type titanium oxide.
【００１８】次に、直径６μｍのＥガラス繊維モノフィ
ラメント（組成：ＳｉＯ2 ：５２〜５６％、Ａｌ
2 Ｏ3 ：１２〜１６％、ＣａＯ：１５〜２５％、Ｍｇ
Ｏ：０〜６％、Ｂ2 Ｏ3 ：８〜１３％、Ｎａ2 Ｏ＋Ｋ2
Ｏ：０〜１％）に上記の方法で作製した触媒繊維（直径
５μｍ）を混紡率２０ｗｔ％とし、打ち込み密度８５０
ｇ／ｍ 2 で綾織に織り上げてフィルタを作製した後、フ
ッ化エチレン系樹脂：６ｗｔ％、カーボン：３ｗｔ％、
シリコーン：２ｗｔ％含有する処理液に浸漬し、絞りロ
ーラで処理液を除いてから乾燥した。Next, an E glass fiber monolith having a diameter of 6 μm was used.
Lament (composition: SiOTwo: 52-56%, Al
TwoOThree: 12 to 16%, CaO: 15 to 25%, Mg
O: 0-6%, BTwoOThree: 8-13%, NaTwoO + KTwo
O: 0 to 1%) in the catalyst fiber (diameter) produced by the above method.
5 μm) with a blending ratio of 20 wt% and an implantation density of 850
g / m TwoAfter fabricating the filter by weaving into a twill weave,
Ethylene-based resin: 6 wt%, carbon: 3 wt%,
Silicone: Immerse in a processing solution containing 2 wt% and squeeze
After removing the treating solution with a roller, drying was performed.
【００１９】このフィルタをＮＯ：１００ｐｐｍ、ＮＨ
3 ：８０ｐｐｍ、ＳＯ2 ：５０ｐｐｍ、ＨＣ（炭化水
素）：１２００ｐｐｍ、Ｈ2 Ｏ：２０％およびふんじ
ん：１０ｇ／Ｎｍ3 を含有する２３０℃の排ガスを１１
／分のガス量で導入して脱硝試験を行ったところ、脱硝
率の値は８０％であった。また除塵率は９９．９％であ
った。This filter is provided with NO: 100 ppm, NH
3: 80ppm, SO 2: 50ppm , HC ( hydrocarbon): 1200ppm, H 2 O: 20% and dust: a 230 ° C. exhaust gas containing 10 g / Nm 3 11
When a denitration test was performed by introducing gas at a rate of / min, the value of the denitration rate was 80%. The dust removal rate was 99.9%.
【００２０】（実施例２）まず、市販のシリコンメトキ
シド１２６ｇに、ＨＣｌを０．３ｇおよびＨ2 Ｏを２２
ｇおよびエタノール１２６ｇを混合した液を攪拌しなが
ら滴下混合した後、８０℃で２時間攪拌を続けた。２時
間経過後チタンイソプロポキシド：１６８ｇを加えてさ
らに２時間加熱攪拌した後、この溶液を０℃に冷却し、
Ｈ2 Ｏ：１６ｇおよびエタノール：１６８ｇからなる混
合液を攪拌しながら混合した。これを再び８０℃で２時
間攪拌し、三塩化バナジル：４．９ｇを混合して、さら
に８０℃で２時間攪拌した後、減圧濃縮してアルコール
を除去して紡糸可能な粘稠液を調製した。Example 2 First, 0.3 g of HCl and 22 g of H 2 O were added to 126 g of commercially available silicon methoxide.
g and 126 g of ethanol were added dropwise while stirring, and then stirring was continued at 80 ° C. for 2 hours. After 2 hours, 168 g of titanium isopropoxide was added, and the mixture was further heated and stirred for 2 hours. Thereafter, the solution was cooled to 0 ° C.
A mixed solution consisting of 16 g of H 2 O and 168 g of ethanol was mixed with stirring. This was again stirred at 80 ° C. for 2 hours, mixed with 4.9 g of vanadyl trichloride, further stirred at 80 ° C. for 2 hours, and concentrated under reduced pressure to remove alcohol to prepare a viscous liquid capable of spinning. did.
【００２１】この粘稠液から繊維を紡糸し、ＳｉＯ2 ：
ＴｉＯ2 ：Ｖ2 Ｏ5 ＝５０：４７．５：２．５（ｗｔ）
のアモルファス繊維を作製した。このアモルファス繊維
を５００℃で２時間熱処理しアナターゼ型酸化チタンを
１０％含む触媒繊維を作製した。A fiber is spun from this viscous liquid, and SiO 2 :
TiO 2 : V 2 O 5 = 50: 47.5: 2.5 (wt)
Was produced. This amorphous fiber was heat-treated at 500 ° C. for 2 hours to prepare a catalyst fiber containing 10% of anatase type titanium oxide.
【００２２】次に、直径６μｍのＥガラス繊維モノフィ
ラメント（組成：ＳｉＯ2 ：５２〜５６％、Ａｌ
2 Ｏ3 ：１２〜１６％、ＣａＯ：１５〜２５％、Ｍｇ
Ｏ：０〜６％、Ｂ2 Ｏ3 ：８〜１３％、Ｎａ2 Ｏ＋Ｋ2
Ｏ：０〜１％）に上記の方法で作製した触媒繊維（直径
５μｍ）を混紡率２０ｗｔ％とし、打ち込み密度８５０
ｇ／ｍ 2 で綾織に織り上げてフィルタを作製した後、フ
ッ化エチレン系樹脂：６ｗｔ％、カーボン：３ｗｔ％、
シリコーン：２ｗｔ％含有する処理液に浸漬し、絞りロ
ーラで処理液を除いてから乾燥した。Next, an E glass fiber monofilament having a diameter of 6 μm was used.
Lament (composition: SiOTwo: 52-56%, Al
TwoOThree: 12 to 16%, CaO: 15 to 25%, Mg
O: 0-6%, BTwoOThree: 8-13%, NaTwoO + KTwo
O: 0 to 1%) in the catalyst fiber (diameter) produced by the above method.
5 μm) with a blending ratio of 20 wt% and an implantation density of 850
g / m TwoAfter fabricating the filter by weaving into a twill weave,
Ethylene-based resin: 6 wt%, carbon: 3 wt%,
Silicone: Immerse in a processing solution containing 2 wt% and squeeze
After removing the treating solution with a roller, drying was performed.
【００２３】このフィルタをＮＯ：１００ｐｐｍ、ＮＨ
3 ：８０ｐｐｍ、ＳＯ2 ：５０ｐｐｍ、ＨＣ：１２００
ｐｐｍ、Ｈ2 Ｏ：２０％およびふんじん：１０ｇ／Ｎｍ
3 を含有する２３０℃の排ガスを１１／分のガス量で導
入して脱硝試験を行ったところ、脱硝率の値は８０％で
あった。また除塵率は９９．９％であった。This filter is provided with NO: 100 ppm, NH
3 : 80 ppm, SO 2 : 50 ppm, HC: 1200
ppm, H 2 O: 20% and dust: 10 g / Nm
When a denitration test was performed by introducing an exhaust gas at 230 ° C. containing 3 at a gas amount of 11 / min, the value of the denitration rate was 80%. The dust removal rate was 99.9%.
【００２４】（実施例３）まず、市販のチタンイソプロ
ポキシド３４１ｇとエタノール１７０ｇを混合した液を
０℃に冷却し、これにＨＣ：１０．４４ｇおよびＨ
2 Ｏ：３２ｇおよびエタノール：１７０ｇからなる混合
液を攪拌しながら混合した。これを８０℃で２時間攪拌
し、バナジルテトラｎ−プロポキシド：１３ｇを混合し
てさらに８０℃で２時間攪拌した後、減圧濃縮してアル
コールを除去して紡糸可能な粘稠液を調製した。Example 3 First, a liquid obtained by mixing 341 g of commercially available titanium isopropoxide and 170 g of ethanol was cooled to 0 ° C., and 10.44 g of HC and H
A mixed solution consisting of 32 g of 2O and 170 g of ethanol was mixed with stirring. This was stirred at 80 ° C. for 2 hours, mixed with vanadyl tetra n-propoxide: 13 g, further stirred at 80 ° C. for 2 hours, and concentrated under reduced pressure to remove alcohol to prepare a viscous liquid capable of spinning. .
【００２５】この粘稠液から繊維を紡糸し、ＴｉＯ2 ：
Ｖ2 Ｏ5 ＝９５：５（ｗｔ）のアモルファス繊維を作製
した。このアモルファス繊維を５００℃で２時間熱処理
しアナターゼ型酸化チタンを２０％含む触媒繊維を作製
した。Fibers are spun from this viscous liquid and TiO 2 :
An amorphous fiber of V 2 O 5 = 95: 5 (wt) was produced. This amorphous fiber was heat-treated at 500 ° C. for 2 hours to prepare a catalyst fiber containing 20% of anatase type titanium oxide.
【００２６】次に、直径６μｍのＥガラス繊維モノフィ
ラメント（組成：ＳｉＯ2 ：５２〜５６％、Ａｌ
2 Ｏ3 ：１２〜１６％、ＣａＯ：１５〜２５％、Ｍｇ
Ｏ：０〜６％、Ｂ2 Ｏ3 ：８〜１３％、Ｎａ2 Ｏ＋Ｋ2
Ｏ：０〜１％）に上記の方法で作製した触媒繊維（直径
５μｍ）を混紡率２０ｗｔ％とし、打ち込み密度８５０
ｇ／ｍ 2 で綾織に織り上げてフィルタを作製した後、フ
ッ化エチレン系樹脂：６ｗｔ％、カーボン：３ｗｔ％、
シリコーン：２ｗｔ％含有する処理液に浸漬し、絞りロ
ーラで処理液を除いてから乾燥した。Next, a monofilament of E glass fiber having a diameter of 6 μm was used.
Lament (composition: SiOTwo: 52-56%, Al
TwoOThree: 12 to 16%, CaO: 15 to 25%, Mg
O: 0-6%, BTwoOThree: 8-13%, NaTwoO + KTwo
O: 0 to 1%) in the catalyst fiber (diameter) produced by the above method.
5 μm) with a blending ratio of 20 wt% and an implantation density of 850
g / m TwoAfter fabricating the filter by weaving into a twill weave,
Ethylene-based resin: 6 wt%, carbon: 3 wt%,
Silicone: Immerse in a processing solution containing 2 wt% and squeeze
After removing the treating solution with a roller, drying was performed.
【００２７】このフィルタをＮＯ：１００ｐｐｍ、ＮＨ
3 ：８０ｐｐｍ、ＳＯ2 ：５０ｐｐｍ、ＨＣ：１２００
ｐｐｍ、Ｈ2 Ｏ：２０％およびふんじん：１０ｇ／Ｎｍ
3 を含有する２３０℃の排ガスを１１／分のガス量で導
入して脱硝試験を行ったところ、脱硝率の値は８２％で
あった。また除塵率は９９．９％であった。This filter was set to NO: 100 ppm, NH
3 : 80 ppm, SO 2 : 50 ppm, HC: 1200
ppm, H 2 O: 20% and dust: 10 g / Nm
When a denitration test was conducted by introducing an exhaust gas at 230 ° C. containing 3 at a gas amount of 11 / min, the value of the denitration rate was 82%. The dust removal rate was 99.9%.
【００２８】（実施例４）まず、市販のチタンイソプロ
ポキシド３４１ｇとエタノール１７０ｇを混合した液を
０℃に冷却し、これにＨＣ：１０．４４ｇおよびＨ
2 Ｏ：３２ｇおよびエタノール：１７０ｇからなる混合
液を攪拌しながら混合した。これを８０℃で２時間攪拌
し、三塩化バナジル：９．４ｇを混合してさらに８０℃
で２時間攪拌した後、減圧濃縮してアルコールを除去し
て紡糸可能な粘稠液を調製した。Example 4 First, a liquid obtained by mixing 341 g of commercially available titanium isopropoxide and 170 g of ethanol was cooled to 0 ° C., and 10.44 g of HC and H
A mixed solution consisting of 32 g of 2O and 170 g of ethanol was mixed with stirring. This was stirred at 80 ° C. for 2 hours, mixed with 9.4 g of vanadyl trichloride, and further mixed at 80 ° C.
After stirring for 2 hours, alcohol was removed by vacuum concentration to prepare a viscous liquid that can be spun.
【００２９】この粘稠液から繊維を紡糸し、ＴｉＯ2 ：
Ｖ2 Ｏ5 ＝９５：５（ｗｔ）のアモルファス繊維を作製
した。このアモルファス繊維を５００℃で２時間熱処理
しアナターゼ型酸化チタンを２０％含む触媒繊維を作製
した。Fibers are spun from this viscous liquid and TiO 2 :
An amorphous fiber of V 2 O 5 = 95: 5 (wt) was produced. This amorphous fiber was heat-treated at 500 ° C. for 2 hours to prepare a catalyst fiber containing 20% of anatase type titanium oxide.
【００３０】次に、直径６μｍのＥガラス繊維モノフィ
ラメント（組成：ＳｉＯ2 ：５２〜５６％、Ａｌ
2 Ｏ3 ：１２〜１６％、ＣａＯ：１５〜２５％、Ｍｇ
Ｏ：０〜６％、Ｂ2 Ｏ3 ：８〜１３％、Ｎａ2 Ｏ＋Ｋ2
Ｏ：０〜１％）に上記の方法で作製した触媒繊維（直径
５μｍ）を混紡率２０ｗｔ％とし、打ち込み密度８５０
ｇ／ｍ 2 で綾織に織り上げてフィルタを作製した後、フ
ッ化エチレン系樹脂：６ｗｔ％、カーボン：３ｗｔ％、
シリコーン：２ｗｔ％含有する処理液に浸漬し、絞りロ
ーラで処理液を除いてから乾燥した。Next, an E glass fiber monofilament having a diameter of 6 μm was used.
Lament (composition: SiOTwo: 52-56%, Al
TwoOThree: 12 to 16%, CaO: 15 to 25%, Mg
O: 0-6%, BTwoOThree: 8-13%, NaTwoO + KTwo
O: 0 to 1%) in the catalyst fiber (diameter) produced by the above method.
5 μm) with a blending ratio of 20 wt% and an implantation density of 850
g / m TwoAfter fabricating the filter by weaving into a twill weave,
Ethylene-based resin: 6 wt%, carbon: 3 wt%,
Silicone: Immerse in a processing solution containing 2 wt% and squeeze
After removing the treating solution with a roller, drying was performed.
【００３１】このフィルタをＮＯ：１００ｐｐｍ、ＮＨ
3 ：８０ｐｐｍ、ＳＯ2 ：５０ｐｐｍ、ＨＣ：１２００
ｐｐｍ、Ｈ2 Ｏ：２０％およびふんじん：１０ｇ／Ｎｍ
3 を含有する２３０℃の排ガスを１１／分のガス量で導
入して脱硝試験を行ったところ、脱硝率の値は８２％で
あった。また除塵率は９９．９％であった。This filter was set to NO: 100 ppm, NH
3 : 80 ppm, SO 2 : 50 ppm, HC: 1200
ppm, H 2 O: 20% and dust: 10 g / Nm
When a denitration test was conducted by introducing an exhaust gas at 230 ° C. containing 3 at a gas amount of 11 / min, the value of the denitration rate was 82%. The dust removal rate was 99.9%.
【００３２】[0032]
【発明の効果】本発明によれば、アモルファス繊維を熱
処理することにより、アナターゼ型酸化チタンを一部析
出させた触媒繊維が得られるため、使用中にもアナター
ゼ型結晶が徐々に析出する。そのためこの触媒繊維を混
紡して得られるフィルタは脱硝と除塵を同時に行うこと
ができ、さらに触媒が被毒された場合でも新たなアナタ
ーゼが順次析出するため長期に渡って脱硝率が安定す
る。According to the present invention, a catalyst fiber in which anatase-type titanium oxide is partially deposited can be obtained by heat-treating an amorphous fiber, so that anatase-type crystals gradually precipitate during use. Therefore, a filter obtained by blending the catalyst fiber can simultaneously perform denitration and dust removal, and even if the catalyst is poisoned, new anatase is sequentially deposited, so that the denitration rate is stable for a long period of time.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 川島 孝一 岐阜県不破郡垂井町630 日本無機株式 会社垂井工場内 (72)発明者 増田 竜司 岐阜県不破郡垂井町630 日本無機株式 会社垂井工場内 (72)発明者 井上 保夫 神奈川県横浜市中区錦町12番地 菱日エ ンジニアリング株式会社システム事業部 内 (56)参考文献 特開 昭56−147632（ＪＰ，Ａ) 特開 昭61−212335（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 37/36 B01D 39/00 B01D 53/86 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Koichi Kawashima 630, Tarui-cho, Fuwa-gun, Gifu Prefecture Japan Inorganic Co., Ltd. 72) Inventor Yasuo Inoue 12 Nishiki-cho, Naka-ku, Yokohama-shi, Kanagawa Prefecture, Ryohichi Engineering Co., Ltd. System Division (56) References JP-A-56-147632 (JP, A) JP-A-61-212335 (JP) , A) (58) Fields investigated (Int. Cl. 7 , DB name) B01J 21/00-37/36 B01D 39/00 B01D 53/86
Claims (3)
合物、あるいはチタンアルコキシドおよびバナジウム化
合物と他のアルコキシドとの混合アルコキシド溶液を加
水分解しゲル化させるゾルゲル法により作製したアモル
ファス繊維を熱処理し、アナターゼ型酸化チタンと酸化
バナジウムの結晶を析出させることによって得られるア
モルファス酸化チタン相とアナターゼ型酸化チタン相が
共存し、かつ酸化バナジウムを含む繊維であることを特
徴とする触媒繊維。1. Titanium alkoxide and vanadium conversion
Compound, or titanium alkoxide and vanadium
Add a mixed alkoxide solution of the compound and another alkoxide.
Amole prepared by the sol-gel method of hydrolyzing and gelling
Heat treatment of facsimile fiber and oxidation with anatase type titanium oxide
A obtained by depositing vanadium crystals.
The morphous titanium oxide phase and the anatase type titanium oxide phase
A catalyst fiber which coexists and is a fiber containing vanadium oxide.
であり、かつ酸化バナジウムの含有率が１〜５ｗｔ％で
あることを特徴とする請求項１記載の触媒繊維。2. The content of titanium oxide is 20 to 95% by weight.
The catalyst fiber according to claim 1, wherein the content of vanadium oxide is 1 to 5 wt%.
ることを特徴とする請求項１又は２記載の触媒繊維。3. The catalyst fiber according to claim 1, wherein the crystallization ratio of anatase is 10% or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00647292A JP3228983B2 (en) | 1992-01-17 | 1992-01-17 | Catalytic fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00647292A JP3228983B2 (en) | 1992-01-17 | 1992-01-17 | Catalytic fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05184923A JPH05184923A (en) | 1993-07-27 |
| JP3228983B2 true JP3228983B2 (en) | 2001-11-12 |
Family
ID=11639404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP00647292A Expired - Fee Related JP3228983B2 (en) | 1992-01-17 | 1992-01-17 | Catalytic fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3228983B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6086844A (en) | 1996-12-26 | 2000-07-11 | Sumitomo Chemical Company, Ltd. | Titania fiber, method for producing the fiber and method for using the fiber |
| DE19906042A1 (en) * | 1998-02-13 | 1999-09-02 | Sumitomo Chemical Co | Production of titanium dioxide fibers containing catalyst, useful for removing nitrogen oxides, organic compounds etc. |
| CN114699845B (en) * | 2022-04-15 | 2023-05-23 | 西南化工研究设计院有限公司 | Preparation method and application of denitration and dust removal integrated filter material |
-
1992
- 1992-01-17 JP JP00647292A patent/JP3228983B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05184923A (en) | 1993-07-27 |
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