JPH05184923A - Catalyst fiber - Google Patents
Catalyst fiberInfo
- Publication number
- JPH05184923A JPH05184923A JP4006472A JP647292A JPH05184923A JP H05184923 A JPH05184923 A JP H05184923A JP 4006472 A JP4006472 A JP 4006472A JP 647292 A JP647292 A JP 647292A JP H05184923 A JPH05184923 A JP H05184923A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- fiber
- titanium oxide
- amorphous
- filter
- 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
- 239000000835 fiber Substances 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 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 abstract description 10
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- 230000008025 crystallization Effects 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 239000007788 liquid Substances 0.000 description 18
- 239000000428 dust Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 12
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- -1 titanium alkoxide Chemical class 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 150000004703 alkoxides Chemical class 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 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
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 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
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 150000003682 vanadium compounds Chemical class 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
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012717 electrostatic precipitator Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 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
- 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
- 239000000460 chlorine 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
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 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
- 239000011259 mixed solution 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
- 238000003980 solgel method Methods 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
- 239000002699 waste material Substances 0.000 description 1
Abstract
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 catalyst fiber useful as a structural material for a catalyst filter used in an exhaust gas treatment apparatus such as an municipal waste incinerator, a sewage pollution incinerator, an industrial waste incinerator, a boiler and a diesel engine, A catalyst filter using the catalyst fiber of the present invention is used for nitrogen oxides and dust in exhaust gas, and further for 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 electrostatic precipitator (EP), a cyclone, a venturi claver, a bag filter and the like have been used to remove 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 soot and dust, and it is necessary to install a dust collector and a denitration device together to remove them. Further, fibers of E glass or S glass are 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。DISCLOSURE OF THE INVENTION The present invention is intended to provide a catalyst fiber as a structural material of a catalyst filter, which enables denitration, dust removal, and acid gas removal to be performed by a single treatment apparatus. is there.
【０００４】[0004]
【課題を解決するための手段】本発明は （１）アナターゼ型酸化チタンおよび酸化バナジウムを
含む繊維であることを特徴とする触媒繊維。The present invention provides (1) a catalyst fiber comprising a fiber containing anatase type titanium oxide and 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 w
t%, and the vanadium oxide content is 1 to 5 wt.
%, The catalyst fiber according to (1) above.
【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。である。(3) The catalyst fiber according to the above (1) or (2), characterized in that the crystallization rate of anatase is 10% or more. Is.
【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 anatase type obtained by heat-treating an amorphous fiber prepared by a sol-gel method in which a solution of titanium alkoxide and vanadium compound or a mixed alkoxide solution of titanium alkoxide and vanadium compound and other alkoxide is hydrolyzed and gelled. It is obtained by precipitating 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。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. The vanadium compound may be any one that is soluble in the alcohol used as the solvent, and for example, vanadyl alkoxide or vanadyl chloride 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。Further, in the case of producing a composite alkoxide, an alkoxide of an oxide, which is likely to be a skeleton material of amorphous fibers, such as silicon alkoxide, aluminum alkoxide, boron alkoxide, etc. can be used.
Among the silicon alkoxides, silicon methoxide or silicon ethoxide is preferable 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 above alkoxide solution is hydrolyzed, amorphous fibers are spun, and then heat treated to precipitate crystals of anatase-type titanium oxide and vanadium oxide. The heat treatment temperature is preferably a temperature at which anatase crystals having slow crystallization are deposited, that is, a range of 200 to 700 ° C, and particularly 350 ° C 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 crystal, the crystallization rate is preferably 10 to 90%, and 30 to 50% of the crystallized fiber is preferable.
【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 larger the catalyst content in the fiber, the better. However, when considering the ease of producing amorphous fibers, 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 weight ratio of titanium oxide to vanadium oxide is preferably about 95: 5 to 80:10.
【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、触媒機能にはアモルファス
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。In the catalyst fiber of the present invention, anatase-type titanium oxide and vanadium oxide effective for denitration are deposited, and when a filter is formed by using this fiber, a catalyst 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 lowered due to various factors and the denitration rate is lowered. However, since the catalyst fiber of the present invention is a method of heat-treating amorphous fiber to precipitate crystals, the amorphous titanium oxide phase and the anatase type titanium oxide phase coexist in the catalytic function, and the amorphous titanium oxide phase is caused by the thermal energy during use. Is gradually transferred to anatase-type titanium oxide, so that a new anatase crystal is deposited even if the anatase-type titanium oxide that is the catalyst component is poisoned. Therefore, the denitration rate does not decrease due to 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 fibers are close to those of ordinary glass fibers and show large values. However, if heat treatment is sufficiently performed to transform all the amorphous fibers into crystals, the fibers become polycrystalline, and the strength of the fibers decreases due to the grain boundaries of the crystals. Therefore, when heat treating the amorphous fibers to precipitate anatase, it is necessary to partially crystallize them so that the amorphous and anatase 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
A solution obtained by mixing 0.3 g of HCl, 22 g of H 2 O and 126 g of ethanol was added dropwise to the mixture 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 heated and stirred for another 2 hours, then, this solution was cooled to 0 ° C. and H 2 O: 16.
g and ethanol: 168 g of a mixed solution was mixed with stirring. This is again stirred at 80 ° C. for 2 hours, vanadyl tetra-n-propoxide: 6.8 g is mixed,
After further stirring at 80 ° C. for 2 hours, the mixture was concentrated under reduced pressure to remove alcohol and 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。Fibers were spun from this viscous liquid to give SiO 2 :
TiO 2 : V 2 O 5 = 50: 47.5: 2.5 (wt)
The amorphous fiber of 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, E glass fiber monofilament having a diameter of 6 μm
Lament (Composition: SiO2: 52-56%, Al
2O3: 12-16%, CaO: 15-25%, Mg
O: 0 to 6%, B2O3: 8 to 13%, Na2O + K2
O: 0 to 1%) and the catalyst fibers (diameter produced by the above method
5 μm) with a blending ratio of 20 wt% and a shot density of 850
g / m 2After weaving it into a twill weave to make a filter,
Ethylene fluoride resin: 6 wt%, carbon: 3 wt%,
Silicone: Immerse in the processing liquid containing 2 wt% and squeeze
The treatment liquid was removed with a filter and dried.
【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 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 conducted by introducing a gas amount of 1 / min, 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 heated and stirred for another 2 hours, and then this solution was cooled to 0 ° C.
A mixture consisting of 16 g of H 2 O and 168 g of ethanol was mixed with stirring. This was stirred again at 80 ° C. for 2 hours, vanadyl trichloride (4.9 g) was mixed, further stirred at 80 ° C. for 2 hours, and then 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。Fibers were spun from this viscous liquid to give SiO 2 :
TiO 2 : V 2 O 5 = 50: 47.5: 2.5 (wt)
The amorphous fiber of 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, E glass fiber monofilament having a diameter of 6 μm
Lament (Composition: SiO2: 52-56%, Al
2O3: 12-16%, CaO: 15-25%, Mg
O: 0 to 6%, B2O3: 8 to 13%, Na2O + K2
O: 0 to 1%) catalyst fiber (diameter produced by the above method
5 μm) with a blending ratio of 20 wt% and a shot density of 850
g / m 2After weaving it into a twill weave to make a filter,
Ethylene fluoride resin: 6 wt%, carbon: 3 wt%,
Silicone: Immerse in the processing liquid containing 2 wt% and squeeze
The treatment liquid was removed with a filter and dried.
【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 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 of 230 ° C. containing 3 at a gas amount of 11 / min, the denitration rate value 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 HC: 10.44 g and H were added thereto.
A mixture of 2 O: 32 g and ethanol: 170 g was mixed with stirring. This was stirred at 80 ° C. for 2 hours, mixed with 13 g of vanadyl tetra-n-propoxide, further stirred at 80 ° C. for 2 hours, and then 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 were spun from this viscous liquid to give TiO 2 :
Amorphous fibers with V 2 O 5 = 95: 5 (wt) were 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, E glass fiber monofilament having a diameter of 6 μm
Lament (Composition: SiO2: 52-56%, Al
2O3: 12-16%, CaO: 15-25%, Mg
O: 0 to 6%, B2O3: 8 to 13%, Na2O + K2
O: 0 to 1%) and the catalyst fibers (diameter produced by the above method
5 μm) with a blending ratio of 20 wt% and a shot density of 850
g / m 2After weaving it into a twill weave to make a filter,
Ethylene fluoride resin: 6 wt%, carbon: 3 wt%,
Silicone: Immerse in the processing liquid containing 2 wt% and squeeze
The treatment liquid was removed with a filter and dried.
【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 is 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 containing 230 at 230 ° C. at a gas amount of 11 / min, the denitration rate value 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 HC: 10.44 g and H were added thereto.
A mixture of 2 O: 32 g and ethanol: 170 g was mixed with stirring. This is stirred at 80 ° C for 2 hours, mixed with vanadyl trichloride (9.4g) and further heated at 80 ° C.
After stirring for 2 hours, the mixture was concentrated under reduced pressure to remove alcohol to prepare a viscous liquid capable of spinning.
【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 were spun from this viscous liquid to give TiO 2 :
Amorphous fibers with V 2 O 5 = 95: 5 (wt) were 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, E glass fiber monofilament having a diameter of 6 μm was used.
Lament (Composition: SiO2: 52-56%, Al
2O3: 12-16%, CaO: 15-25%, Mg
O: 0 to 6%, B2O3: 8 to 13%, Na2O + K2
O: 0 to 1%) and the catalyst fibers (diameter produced by the above method
5 μm) with a blending ratio of 20 wt% and a shot density of 850
g / m 2After weaving it into a twill weave to make a filter,
Ethylene fluoride resin: 6 wt%, carbon: 3 wt%,
Silicone: Immerse in the processing liquid containing 2 wt% and squeeze
The treatment liquid was removed with a filter and dried.
【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 is 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 containing 230 at 230 ° C. at a gas amount of 11 / min, the denitration rate value 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。EFFECTS OF THE INVENTION According to the present invention, a catalyst fiber in which anatase-type titanium oxide is partially deposited is obtained by heat-treating an amorphous fiber, so that anatase-type crystals gradually precipitate even during use. Therefore, the filter obtained by mixing and spinning this catalyst fiber can perform denitration and dust removal at the same time, and even when 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 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koichi Kawashima 630 Tarui-cho, Fuwa-gun, Gifu Prefecture, Japan Inorganic Stock Company Tarui factory (72) Inventor Ryuji Masuda 630 Tarui-cho, Fuwa-gun, Gifu Japan Tarui factory (72) Inventor Yasuo Inoue 12 Nishiki-cho, Naka-ku, Yokohama-shi, Kanagawa Ryohichi Engineering Co., Ltd. System Division
Claims (3)
ジウムを含む繊維であることを特徴とする触媒繊維。1. A catalyst fiber comprising a fiber containing anatase type titanium oxide and 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 wt%.
And the vanadium oxide content is 1 to 5 wt%, and the catalyst fiber according to claim 1.
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 rate 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 true JPH05184923A (en) | 1993-07-27 |
| JP3228983B2 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) |
Cited By (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 |
| US6162759A (en) * | 1998-02-13 | 2000-12-19 | Sumitomo Chemical Company, Ltd. | Method for producing a catalyst component-carrying titania fiber |
| CN114699845A (en) * | 2022-04-15 | 2022-07-05 | 西南化工研究设计院有限公司 | Preparation method and application of denitration and dedusting integrated filter material |
-
1992
- 1992-01-17 JP JP00647292A patent/JP3228983B2/en not_active Expired - Fee Related
Cited By (5)
| 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 |
| US6191067B1 (en) | 1996-12-26 | 2001-02-20 | Sumitomo Chemical, Ltd. | Titania fiber, method for producing the fiber and method for using the fiber |
| US6409961B1 (en) | 1996-12-26 | 2002-06-25 | Sumitomo Chemical Co., Ltd. | Titania fiber, method for producing the fiber and method for using the fiber |
| US6162759A (en) * | 1998-02-13 | 2000-12-19 | Sumitomo Chemical Company, Ltd. | Method for producing a catalyst component-carrying titania fiber |
| CN114699845A (en) * | 2022-04-15 | 2022-07-05 | 西南化工研究设计院有限公司 | Preparation method and application of denitration and dedusting integrated filter material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3228983B2 (en) | 2001-11-12 |
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