JPH0977511A - Titanium-containing mordenite and its production - Google Patents
Titanium-containing mordenite and its productionInfo
- Publication number
- JPH0977511A JPH0977511A JP25941995A JP25941995A JPH0977511A JP H0977511 A JPH0977511 A JP H0977511A JP 25941995 A JP25941995 A JP 25941995A JP 25941995 A JP25941995 A JP 25941995A JP H0977511 A JPH0977511 A JP H0977511A
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- surface area
- source
- mordenite
- containing mordenite
- 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.)
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- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、チタン含有モルデナイ
トおよびその製造方法に関し、さらに詳しくは、微細な
針状結晶（形状）を有し、大きい外部比表面積を有する
チタン含有モルデナイトおよびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a titanium-containing mordenite and a method for producing the same, and more particularly to a titanium-containing mordenite having fine acicular crystals (shape) and a large external specific surface area and a method for producing the same. .
【０００２】[0002]
【従来技術およびその問題点】近年、触媒や吸着剤など
の用途に新しい機能を持たせたゼオライトの合成研究が
盛んで、ゼオライト中のＡｌあるいはＳｉをＧａ、Ｆ
ｅ、ＢやＧｅ、Ｔｉなどの他の原子で置換したゼオライ
トが合成されている。特開平５−２４８２０号公報に
は、モルデナイト構造のＸ線回折パターンを示し、か
つ、赤外吸収スペクトルにおいて９６０ｃｍ-1付近の吸
収を示すチタン含有アルミノシリケートゼオライトが開
示されており、また、シリカ源、チタン源、アルミナ
源、アルカリ源、有機アルキルアンモニウム化合物およ
び／またはカルボキシル基を有する有機化合物を含む特
定組成の水性反応混合物をゼオライトの結晶化条件で反
応させるモルデナイト構造を有するチタン含有アルミノ
シリケートゼオライトの製造方法が記載されている。し
かし、従来のチタン含有モルデナイトは、外部表面積が
小さいため、触媒や吸着剤などに使用した場合に必ずし
も満足のいく効果が得られなかった。2. Description of the Related Art In recent years, a great deal of research has been conducted on the synthesis of zeolite having a new function for use as a catalyst, an adsorbent, etc., and Al or Si in the zeolite has a Ga or F content.
Zeolites substituted with other atoms such as e, B, Ge, and Ti have been synthesized. Japanese Unexamined Patent Publication (Kokai) No. 5-24820 discloses a titanium-containing aluminosilicate zeolite which exhibits an X-ray diffraction pattern of a mordenite structure and exhibits an absorption near 960 cm -1 in an infrared absorption spectrum, and a silica source. A titanium-containing aluminosilicate zeolite having a mordenite structure in which an aqueous reaction mixture having a specific composition containing a titanium source, an alumina source, an alkali source, an organic alkylammonium compound and / or an organic compound having a carboxyl group is reacted under zeolite crystallization conditions. Manufacturing methods are described. However, since conventional titanium-containing mordenite has a small external surface area, a satisfactory effect is not always obtained when it is used as a catalyst or an adsorbent.
【０００３】[0003]
【本発明の目的】本発明の目的は、モルデナイト骨格構
造中にＴｉ原子を含有し、かつ全表面積に対し外部表面
積の占める割合の高いモルデナイトおよびその製造方法
を提供することにある。An object of the present invention is to provide mordenite containing Ti atoms in the mordenite skeleton structure and having a high proportion of the external surface area to the total surface area, and a method for producing the same.
【０００４】[0004]
【発明の構成】本発明の第１は、全表面積に対し少なく
とも７％以上の外部表面積を有することを特徴とするチ
タン含有モルデナイトに関する。また、本発明の第２
は、シリカ源、アルミナ源、チタン源およびアルカリ源
が酸化物モル組成で、 Ｍ2Ｏ／Ａｌ2Ｏ3 ＝２．０〜６．０ ＳｉＯ2／Ａｌ2Ｏ3＝１０〜５０ ＴｉＯ2／Ａｌ2Ｏ3＝０．０１〜１．５ Ｈ2Ｏ／Ａｌ2Ｏ3 ＝１５０〜５００ （ここで、Ｍはアルカリ金属を表わす）の範囲にあるゲ
ル状水性反応混合物を、水熱反応によって結晶化させる
ことを特徴とする。前記チタン源は、３価のチタンを含
有するものであることが好ましい。The first aspect of the present invention relates to a titanium-containing mordenite having an external surface area of at least 7% or more based on the total surface area. The second aspect of the present invention
Is a silica source, an alumina source, a titanium source and an alkali source having an oxide molar composition, and M 2 O / Al 2 O 3 = 2.0 to 6.0 SiO 2 / Al 2 O 3 = 10 to 50 TiO 2 / A gel-like aqueous reaction mixture in the range of Al 2 O 3 = 0.01 to 1.5 H 2 O / Al 2 O 3 = 150 to 500 (where M represents an alkali metal) is hydrothermally reacted. It is characterized by being crystallized. The titanium source preferably contains trivalent titanium.
【０００５】以下に本発明を具体的に説明する。前記の
ように本発明のチタン含有モルデナイトの外部表面積の
大きい特徴は図３に示すような走査電顕写真から見てモ
ルデナイトの針状結晶の集合体である針状形状に由来す
るものと推定される。該外部表面積は、全表面積に対し
７％以上、好ましくは９％以上である。前記外部表面積
が７％未満では空間速度が非常に大きい反応の触媒など
に使用した場合に有益性が少ない。また、前記外部表面
積の上限値は、２０％程度である。前記全表面積は、Ｂ
ＥＴ法により測定され、また、外部表面積は、Ｊ．Ｈ．
ＤＥ ＢＯＥＲ ｅｔ ａｌ Ｊｏｕｒｎａｌ ｏｆ
Ｃａｔａｌｙｓｉｓ ４，Ｐ３１９−３２３（１９６
５）に記載されているＶａ−ｔプロット法により測定さ
れる。本発明のチタン含有モルデナイトの他の重要な特
徴は、モルデナイト骨格構造中にＴｉ原子を含有する。
ゼオライト骨格構造中のＴｉ原子の存在は、赤外吸収ス
ペクトルにより確認され、９７０ｃｍ-1付近に吸収ピー
クが現われることが報告されている〔例えば、Ｂ．Ｋａ
ｕｓｈａｒｒ．ｅｔａｌ．ＣａｔａｌｙｓｉｓＬｅｔｔ
ｅｒ，１， ｐ−８１（１９８８）〕が、本発明のチタ
ン含有モルデナイトの赤外吸収スペクトルは、図２に示
すように９６０ｃｍ-1の所に吸収ピークが認められ、Ｔ
ｉ原子がゼオライト骨格構造中に存在することが分か
る。本発明のモルデナイトでは、Ｔｉ原子を酸化物とし
て、０．０１〜１０重量％含有することが望ましい。
０．０１重量％未満では、針状結晶が得られにくく、１
０重量％を越えるとモルデナイトの合成が困難になる。Hereinafter, the present invention will be described specifically. As described above, the feature that the titanium-containing mordenite of the present invention has a large external surface area is presumed to be derived from the acicular shape which is an aggregate of acicular crystals of mordenite as seen from the scanning electron micrograph as shown in FIG. It The external surface area is 7% or more, preferably 9% or more, based on the total surface area. When the external surface area is less than 7%, it is less useful when used as a catalyst for a reaction having a very high space velocity. The upper limit of the external surface area is about 20%. The total surface area is B
It is measured by the ET method, and the external surface area is measured according to J. H.
DE BOER et al Journal of
Catalysis 4, P319-323 (196
It is measured by the Va-t plotting method described in 5). Another important feature of the titanium-containing mordenite of the present invention is the inclusion of Ti atoms in the mordenite framework.
The presence of Ti atoms in the zeolite skeleton structure was confirmed by infrared absorption spectrum, and it has been reported that an absorption peak appears near 970 cm -1 [eg, B. Ka
usharr. et al. Catalysis Lett
er, 1, p-81 (1988)], the infrared absorption spectrum of the titanium-containing mordenite of the present invention shows an absorption peak at 960 cm −1 as shown in FIG.
It can be seen that the i atom is present in the zeolite framework structure. In the mordenite of the present invention, it is desirable to contain 0.01 to 10% by weight of Ti atom as an oxide.
If it is less than 0.01% by weight, it is difficult to obtain needle-shaped crystals, and 1
If it exceeds 0% by weight, it becomes difficult to synthesize mordenite.
【０００６】次に前記チタン含有モルデナイトの製造方
法について以下に述べる。本発明のチタン含有モルデナ
イトの製造方法では、酸化物モル組成比で Ｍ2Ｏ／Ａｌ2Ｏ3 ＝２．０〜６．０ ＳｉＯ2／Ａｌ2Ｏ3＝１０〜５０ ＴｉＯ2／Ａｌ2Ｏ3＝０．０１〜１．５ Ｈ2Ｏ／Ａｌ2Ｏ3 ＝１５０〜５００ （ここで、Ｍはアルカリ金属を表わす）の範囲にあるシ
リカ源、アルミナ源、チタン源およびアルカリ源とのゲ
ル状水性反応混合物を、好ましくは０〜６０℃の温度で
１〜７２時間、撹拌することなく予備熟成し、次いでオ
ートクレーブ中にて１００〜２００℃の温度で２４〜２
００時間、必要に応じて撹拌しながら、水熱反応を行っ
て結晶化させる。本発明で使用するチタン源としては加
水分解可能なチタン化合物ならいずれでも良いが、特
に、三塩化チタンなどの３価のチタンを含むものが好適
に使用される。このチタン源が四塩化チタン、硫酸チタ
ン（IV）等の４価のチタン源を用いた場合には、目的の
高い外部表面積を持つモデナイトが得られないことがあ
るばかりでなく、チタンがモルデナイトの骨格構造外に
存在しやすくなる。他の原料のシリカ源、アルミナ源お
よびアルカリ源としては通常ゼオライト合成に用いられ
るそれぞれの原料が使用可能である。例えば、シリカ源
としては、シリカゾル、珪酸ソーダ、フッ化アルミニウ
ム製造時の副産物である副生シリカ、ヒュームドシリ
カ、もみがらから得られるシリカ、カオリン、ゼオライ
ト合成の回収シリカなどが例示され、アルミナ源として
は、アルミン酸ソーダ、硫酸アルミニウムなどのアルミ
ニウム塩や水酸化アルミニウムなどが使用され、また、
アルカリ源としては、水酸化ナトリウムや水酸化カリウ
ムなどが例示される。Next, a method for producing the titanium-containing mordenite will be described below. According to the method for producing titanium-containing mordenite of the present invention, M 2 O / Al 2 O 3 = 2.0 to 6.0 SiO 2 / Al 2 O 3 = 10 to 50 TiO 2 / Al 2 O in terms of oxide molar composition ratio. Gel with silica source, alumina source, titanium source and alkali source in the range of 3 = 0.01 to 1.5 H 2 O / Al 2 O 3 = 150 to 500 (where M represents an alkali metal). The aqueous reaction mixture is preferably aged without stirring for 1 to 72 hours at a temperature of 0 to 60 ° C., then in an autoclave at a temperature of 100 to 200 ° C. for 24 to 2
A hydrothermal reaction is carried out for crystallization for 00 hours with stirring, if necessary. As the titanium source used in the present invention, any hydrolyzable titanium compound may be used. In particular, a material containing trivalent titanium such as titanium trichloride is preferably used. When a tetravalent titanium source such as titanium tetrachloride or titanium (IV) sulfate is used as the titanium source, not only the desired modendite having a high external surface area may not be obtained, but titanium may be converted into mordenite. It tends to exist outside the skeletal structure. As the silica source, the alumina source and the alkali source of other raw materials, the respective raw materials usually used for zeolite synthesis can be used. For example, as a silica source, silica sol, sodium silicate, by-product silica that is a by-product during the production of aluminum fluoride, fumed silica, silica obtained from chaff, kaolin, recovered silica of zeolite synthesis, etc. are exemplified. As for, aluminum salts such as sodium aluminate, aluminum sulfate, aluminum hydroxide, etc. are used.
Examples of the alkali source include sodium hydroxide and potassium hydroxide.
【０００７】前記原料の混合方法は特に限定されない
が、チタン源は予めシリカ源と混合し、均一になるまで
十分撹拌することが望ましい。ゲル状水性反応混合物
は、例えば、珪酸ソーダの水溶液に三塩化チタンを添加
し、出来たゲル状混合物にアルミン酸ソーダと水酸化ナ
トリウムを添加して得ることができる。また予めアルミ
ン酸ソーダと水酸化ナトリウムを混合しておき、これに
シリカゾルと三塩化チタンを混合することによって得ら
れたゲル状物を添加する等の方法で得ることが出来る。
本発明では、前述のゲル状水性反応混合物を高温で水熱
反応により結晶化させる前に結晶化の起こりにくい低
温、０〜６０℃、好ましくは２０〜４０℃で、好ましく
は撹拌せずに予備熟成を行うことが好ましい。予備熟成
を行なわなかったり不充分な場合は結晶化に長時間を要
したり、結晶度の低下が起こりやすくなる。予備熟成を
終えたゲル状水性反応混合物は周知の方法で結晶化が生
起する温度で結晶化に充分な時間加熱熟成する。この
時、撹拌を行うことが好ましく、撹拌を行なわなかった
場合、目的とする高外部表面積をもつモルデナイトが得
られにくい。加熱熟成により結晶化されたゼオライトは
周知の方法により濾液を分離し、洗浄、乾燥して回収さ
れる。次に本発明を実施例に基づき、具体的に説明す
る。The mixing method of the raw materials is not particularly limited, but it is desirable that the titanium source is mixed with the silica source in advance and sufficiently stirred until it becomes uniform. The gel-like aqueous reaction mixture can be obtained, for example, by adding titanium trichloride to an aqueous solution of sodium silicate, and adding sodium aluminate and sodium hydroxide to the resulting gel-like mixture. Further, it can be obtained by a method of previously mixing sodium aluminate and sodium hydroxide, and then adding a gel-like substance obtained by mixing silica sol and titanium trichloride to this.
In the present invention, before the crystallization of the above-mentioned gel-like aqueous reaction mixture by a hydrothermal reaction at a high temperature, a low temperature at which crystallization is unlikely to occur, 0 to 60 ° C., preferably 20 to 40 ° C., preferably a preliminary operation without stirring It is preferable to perform aging. If pre-aging is not performed or is insufficient, crystallization takes a long time and the crystallinity is likely to decrease. The gelled aqueous reaction mixture that has been pre-aged is heat-aged by a well-known method at a temperature at which crystallization occurs and for a time sufficient for crystallization. At this time, it is preferable to stir, and if the stirring is not performed, it is difficult to obtain the desired mordenite having a high external surface area. Zeolite crystallized by heating and aging is recovered by separating the filtrate by a well-known method, washing and drying. Next, the present invention will be specifically described based on Examples.
【０００８】実施例１ シリカ濃度１９．５ｗｔ％の３号水硝子１６６８．６ｇ
に撹拌しながら２０ｗｔ％の三塩化チタン溶液３４７．
１ｇを加えた。得られたゲル状水性反応混合物に３０ｗ
ｔ％のシリカゾルを１９１５．３ｇ、さらにＮａ2Ｏ
８．５ｗｔ％、Ａｌ2Ｏ3 １１ｗｔ％を含有するアルミ
ン酸ナトリウム溶液９２３．６ｇを加えた。約１０分間
均一になるまで撹拌した後、３０℃で７２時間静置して
予備熟成を行なった。予備熟成後、ゲル状水性反応混合
物をオートクレーブに移して１７５℃で１００時間加温
熟成を行なった。熟成終了後、温度１００℃以下になる
まで冷却した後、反応混合物を取り出し、濾過、洗浄、
乾燥を行ない、Ｎａ型モルデナイトを得た。さらに常法
で２回ＮＨ4イオン交換を行なった後６００℃で２時間
焼成し、Ｈ型のモルデナイト−１を得た。このモルデナ
イト−１について化学分析による組成、ＢＥＴ法による
比表面積、Ｖａ−ｔプロット法による外部表面積を求め
た。その結果を表１に示す。また、図１にＸ線回折パタ
ーンを、図２に赤外吸収スペクトルを、図３に走査電顕
写真を示す。これらに示すように、Ｔｉ原子が骨格に存
在し特異な針状結晶の集合体をした高い外部表面積をも
つモルデナイトが得られた。Example 1 No. 3 water glass 1668.6 g having a silica concentration of 19.5 wt%.
20 wt% titanium trichloride solution 347.
1 g was added. 30 w to the obtained gel-like aqueous reaction mixture
1915.3 g of t% silica sol, and Na 2 O
923.6 g of a sodium aluminate solution containing 8.5 wt% and Al 2 O 3 11 wt% was added. After stirring for about 10 minutes until uniform, the mixture was allowed to stand at 30 ° C. for 72 hours for preliminary aging. After pre-aging, the gel-like aqueous reaction mixture was transferred to an autoclave and aged by heating at 175 ° C. for 100 hours. After the aging, the reaction mixture was taken out, filtered, washed, and cooled to a temperature of 100 ° C. or lower.
After drying, Na-type mordenite was obtained. Further, NH 4 ion exchange was performed twice in the usual way, and then the mixture was baked at 600 ° C. for 2 hours to obtain H-type mordenite-1. The composition of this mordenite-1 was determined by chemical analysis, the specific surface area by the BET method, and the external surface area by the Va-t plot method. Table 1 shows the results. Further, FIG. 1 shows an X-ray diffraction pattern, FIG. 2 shows an infrared absorption spectrum, and FIG. 3 shows a scanning electron micrograph. As shown in these, mordenite having a high external surface area was obtained, in which Ti atoms were present in the skeleton and formed an aggregate of peculiar needle-like crystals.
【０００９】実施例２ シリカ濃度２４ｗｔ％の３号水硝子１９１６．６ｇに撹
拌しながら２０ｗｔ％の三塩化チタン溶液７７１．３ｇ
を加えた。得られたゲル状水性反応混合物にＨ2Ｏ １
８２７．１ｇ、固形シリカ ４４４ｇ、Ｎａ2Ｏ ８．
５ｗｔ％、Ａｌ2Ｏ3 １１．０ｗｔ％を含有するアルミ
ン酸ナトリウム ９２３．６ｇを加え、均一になるまで
充分に撹拌した。ゲル状水性反応混合物を静置下６０℃
で４８時間予備熟成を行い、次いでこれをオートクレー
ブに移して１７５℃で１２０時間加熱熟成を行った。熟
成終了後、温度を１００℃以下に冷却した後、反応混合
物を取り出し、濾過、洗浄、乾燥を行い、Ｎａ型モルデ
ナイトを得た。さらに常法で２回ＮＨ4イオン交換を行
なった後、６００℃で２時間焼成し、Ｈ型のモルデナイ
ト−２を得た。このモルデナイト−２について、化学分
析による組成、ＢＥＴ法による比表面積、Ｖａ−ｔプロ
ット法による外部表面積を求めた結果を表１に示す。Example 2 771.3 g of a 20 wt% titanium trichloride solution was added to 1916.6 g of No. 3 water glass having a silica concentration of 24 wt%.
Was added. H 2 O 1 was added to the resulting gel-like aqueous reaction mixture.
827.1 g, solid silica 444 g, Na 2 O 8.
923.6 g of sodium aluminate containing 5 wt% and 11.0 wt% of Al 2 O 3 was added, and the mixture was sufficiently stirred until it became uniform. The gel-like aqueous reaction mixture is allowed to stand at 60 ° C.
Preliminary aging for 48 hours was carried out, then this was transferred to an autoclave and heat aging was carried out at 175 ° C. for 120 hours. After completion of the aging, the temperature was cooled to 100 ° C. or lower, the reaction mixture was taken out, filtered, washed and dried to obtain Na-type mordenite. Further, NH 4 ion exchange was performed twice in the usual way, and then the mixture was baked at 600 ° C. for 2 hours to obtain H-type mordenite-2. With respect to this mordenite-2, Table 1 shows the results of determining the composition by chemical analysis, the specific surface area by the BET method, and the external surface area by the Va-t plot method.
【００１０】比較例１ Ｈ2Ｏ２７３３．１ｇに４８％ＮａＯＨ水溶液を５１．
５ｇ溶かし、続いてＮａ2Ｏ ８．５ｗｔ％、Ａｌ2Ｏ3
１１．０ｗｔ％を含有するアルミン酸ナトリウム溶液
１１５．９ｇを加えた。次に、テトライソプロピルオル
トチタネート６８．２ｇを徐々に滴下した。その後７０
℃で２０分間溶液を撹拌した。次に水酸化テトラエチル
アンモニウム４０％水溶液２０２．５ｇを徐々に加え、
さらに１時間撹拌した。最後に、含水ケイ酸粉末（６０
％ＳｉＯ2）６０１．０ｇ加えた。このスラリー状の混
合物の組成はモル比で表わして次のとおりであった。 （ＳｉＯ2＋ＴｉＯ2）／Ａｌ2Ｏ3：２５ ＴｉＯ2／ＳｉＯ2 ：０．０４ ＲＮ+／（ＲＮ+＋Ｎａ+） ：０．３０５ ＯＨ-／ＳｉＯ2 ：０．３ Ｈ2Ｏ／ＳｉＯ2 ：３６ （但し、ＲＮ+は水酸化アルキルアンモニウムイオンを
表わす。）Comparative Example 1 H 2 O 2733.1 g was added with 51% 48% NaOH aqueous solution.
5 g was melted, followed by Na 2 O 8.5 wt%, Al 2 O 3
115.9 g of a sodium aluminate solution containing 11.0 wt% was added. Next, 68.2 g of tetraisopropyl orthotitanate was gradually added dropwise. Then 70
The solution was stirred at 0 ° C for 20 minutes. Next, gradually add 202.5 g of a 40% aqueous solution of tetraethylammonium hydroxide,
It was stirred for another hour. Finally, hydrous silicate powder (60
% SiO 2 ) 601.0 g was added. The composition of this slurry-like mixture was as follows in terms of molar ratio. (SiO 2 + TiO 2 ) / Al 2 O 3 : 25 TiO 2 / SiO 2 : 0.04 RN + / (RN + + Na + ): 0.305 OH − / SiO 2 : 0.3 H 2 O / SiO 2 : 36 (where RN + represents an alkylammonium hydroxide ion).
【００１１】これをオートクレーブに移し、十分な撹拌
下、１６０℃で１６８時間反応を行なった。反応後、温
度を１００℃以下に冷却し、反応混合物を取り出し濾
過、洗浄、乾燥を行い、Ｎａ型モルデナイトを得た。さ
らに常法で２回ＮＨ4イオン交換を行なった後、６００
℃で２時間焼成し、Ｈ型のモルデナイト−３を得た。こ
のモルデナイト−３について、化学分析による組成、Ｂ
ＥＴ法による比表面積、Ｖａ−ｔプロット法による外部
表面積を求めた結果を表１に示す。本発明により得られ
たゼオライトに比べて外部表面積の割合が低い結果とな
った。This was transferred to an autoclave and reacted at 160 ° C. for 168 hours with sufficient stirring. After the reaction, the temperature was cooled to 100 ° C. or lower, the reaction mixture was taken out, filtered, washed, and dried to obtain Na-type mordenite. Further, after performing NH 4 ion exchange twice by a conventional method, 600
The mixture was baked at 2 ° C for 2 hours to obtain H-type mordenite-3. About this mordenite-3, the composition by chemical analysis, B
Table 1 shows the results of determining the specific surface area by the ET method and the external surface area by the Va-t plot method. This resulted in a lower proportion of external surface area compared to the zeolite obtained according to the invention.
【００１２】比較例２ 東ソー（株）モルデナイトＨＳＺ−６４０ＨＯＡについ
て化学分析による組成、ＢＥＴ法による比表面積、Ｖａ
−ｔプロット法による外部表面積を求めた結果を表１に
示す。本発明により得られたゼオライトに比べて外部表
面積の割合が低い結果を得た。Comparative Example 2 Mortarite HSZ-640HOA manufactured by Tosoh Corporation was analyzed by chemical analysis, BET specific surface area, and Va.
Table 1 shows the results of determining the external surface area by the -t plot method. As a result, the proportion of the external surface area was lower than that of the zeolite obtained according to the present invention.
【表１】 [Table 1]
【００１３】次に本発明の好ましい実施態様を示す。 １． 全表面積に対し少なくとも７％以上の外部表面積
を有することを特徴とするチタン含有モルデナイト。 ２． 針状結晶の集合体であることを特徴とする前記１
のチタン含有モルデナイト。 ３． ９６０ｃｍ-1付近に赤外吸収スペクトルを有する
前記１又は２のチタン含有モルデナイト。 ４． チタン源が３価のチタンを含むものであって、か
つシリカ源、アルミナ源、チタン源およびアルカリ源が
酸化物モル組成で、 Ｍ2Ｏ／Ａｌ2Ｏ3 ＝２．０〜６．０ ＳｉＯ2／Ａｌ2Ｏ3＝１０〜５０ ＴｉＯ2／Ａｌ2Ｏ3＝０．０１〜１．５ Ｈ2Ｏ／Ａｌ2Ｏ3 ＝１５０〜５００ （ここで、Ｍはアルカリ金属を表わす）の範囲にあるゲ
ル状水性反応混合物を、水熱反応によって結晶化させ
て、製造されたものである前記１、２または３のチタン
含有モルデナイト。 ５． 水熱反応による結晶化前に、結晶化の起こりにく
い低温、０〜６０℃、好ましくは２０〜４０℃で、さら
に好ましくは撹拌せずに予備熟成を行なったものである
前記４のチタン含有モルデナイト。 ６． シリカ源、アルミナ源、チタン源およびアルカリ
源が酸化物モル組成で、 Ｍ2Ｏ／Ａｌ2Ｏ3 ＝２．０〜６．０ ＳｉＯ2／Ａｌ2Ｏ3＝１０〜５０ ＴｉＯ2／Ａｌ2Ｏ3＝０．０１〜１．５ Ｈ2Ｏ／Ａｌ2Ｏ3 ＝１５０〜５００ （ここで、Ｍはアルカリ金属を表わす）の範囲にあるゲ
ル状水性反応混合物を、水熱反応によって結晶化させる
ことを特徴とする前記１〜５のチタン含有モルデナイト
の製造方法。 ７． 水熱反応による結晶化前に、結晶化が起こりにく
い低温、０〜６０℃、好ましくは２０〜４０℃で、さら
に好ましくは撹拌せずに予備熟成を行うものである前記
６のチタン含有モルデナイトの製造方法。 ８． チタン源が３価のチタンを含有することを特徴と
する前記６または７のチタン含有モルデナイトの製造方
法。Next, preferred embodiments of the present invention will be described. 1. A titanium-containing mordenite having an external surface area of at least 7% or more based on the total surface area. 2. 1 which is an aggregate of needle-like crystals
Titanium-containing mordenite. 3. The titanium-containing mordenite according to 1 or 2 above, which has an infrared absorption spectrum near 960 cm -1 . 4. The titanium source contains trivalent titanium, and the silica source, the alumina source, the titanium source and the alkali source have an oxide molar composition, and M 2 O / Al 2 O 3 = 2.0 to 6.0 SiO 2 / Al 2 O 3 = 10 to 50 TiO 2 / Al 2 O 3 = 0.01 to 1.5 H 2 O / Al 2 O 3 = 150 to 500 (where M represents an alkali metal) 1. The titanium-containing mordenite of 1, 2, or 3 above, which is produced by crystallizing the gel-like aqueous reaction mixture according to 1. above by hydrothermal reaction. 5. The titanium-containing mordenite according to 4 above, which is pre-aged at a low temperature at which crystallization does not easily occur, at 0 to 60 ° C., preferably at 20 to 40 ° C., and more preferably without stirring, before crystallization by hydrothermal reaction. . 6. The silica source, the alumina source, the titanium source and the alkali source have an oxide molar composition, and M 2 O / Al 2 O 3 = 2.0 to 6.0 SiO 2 / Al 2 O 3 = 10 to 50 TiO 2 / Al 2 The gel-like aqueous reaction mixture in the range of O 3 = 0.01 to 1.5 H 2 O / Al 2 O 3 = 150 to 500 (where M represents an alkali metal) is crystallized by a hydrothermal reaction. The method for producing a titanium-containing mordenite according to any one of 1 to 5 above. 7. Prior to crystallization by hydrothermal reaction, the titanium-containing mordenite of 6 above, which is pre-aged at a low temperature at which crystallization does not easily occur, 0 to 60 ° C., preferably 20 to 40 ° C., and more preferably without stirring. Production method. 8. The method for producing titanium-containing mordenite according to 6 or 7, wherein the titanium source contains trivalent titanium.
【００１４】[0014]
【効果】本発明のチタン含有モルデナイトは、その骨格
構造中にＴｉ原子を含むため従来のＴｉ原子を含有しな
いモルデナイトと異なる酸特性を有し、また微細な針状
形状を有するため、従来のモルデナイトに比較して外部
表面積が大きいので各種の触媒や吸着剤などに使用した
場合に優れた効果を示し、特に脱硝触媒に使用して好適
である。[Effect] Since the titanium-containing mordenite of the present invention has Ti atoms in its skeletal structure, it has acid characteristics different from those of conventional mordenite that does not contain Ti atoms, and has a fine needle-like shape. Since it has a large external surface area as compared with, it shows an excellent effect when used for various catalysts and adsorbents, and is particularly suitable for use as a denitration catalyst.
【図１】本発明のチタン含有モルデナイト−１のＸ線回
折パターン図である。FIG. 1 is an X-ray diffraction pattern diagram of titanium-containing mordenite-1 of the present invention.
【図２】本発明のチタン含有モルデナイト−１の赤外吸
収スペクトル図である。FIG. 2 is an infrared absorption spectrum diagram of titanium-containing mordenite-1 of the present invention.
【図３】本発明のチタン含有モルデナイト−１の走査電
顕写真である。FIG. 3 is a scanning electron micrograph of titanium-containing mordenite-1 of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 中本 士郎 福岡県北九州市若松区北湊町13−２ 触媒 化成工業株式会社若松工場内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shiro Nakamoto 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu-shi, Fukuoka Prefecture Catalysis Kasei Kogyo Co., Ltd. Wakamatsu factory
Claims (5)
部表面積を有することを特徴とするチタン含有モルデナ
イト。1. A titanium-containing mordenite having an external surface area of at least 7% or more based on the total surface area.
る請求項１記載のチタン含有モルデナイト。2. The titanium-containing mordenite according to claim 1, which is an aggregate of needle-like crystals.
を有する請求項１または２記載のチタン含有モルデナイ
ト。3. The titanium-containing mordenite according to claim 1, which has an infrared absorption spectrum near 960 cm −1 .
アルカリ源が酸化物モル組成で、 Ｍ2Ｏ／Ａｌ2Ｏ3 ＝２．０〜６．０ ＳｉＯ2／Ａｌ2Ｏ3＝１０〜５０ ＴｉＯ2／Ａｌ2Ｏ3＝０．０１〜１．５ Ｈ2Ｏ／Ａｌ2Ｏ3 ＝１５０〜５００ （ここで、Ｍはアルカリ金属を表わす）の範囲にあるゲ
ル状水性反応混合物を、水熱反応によって結晶化させる
ことを特徴とするチタン含有モルデナイトの製造方法。4. A silica source, an alumina source, a titanium source and an alkali source are oxide molar compositions, and M 2 O / Al 2 O 3 = 2.0 to 6.0 SiO 2 / Al 2 O 3 = 10 to 50. A gel-like aqueous reaction mixture in the range of TiO 2 / Al 2 O 3 = 0.01 to 1.5 H 2 O / Al 2 O 3 = 150 to 500 (where M represents an alkali metal) is treated with water. A method for producing titanium-containing mordenite, which comprises crystallizing by thermal reaction.
のであることを特徴とする請求項４記載のチタン含有モ
ルデナイトの製造方法。5. The method for producing titanium-containing mordenite according to claim 4, wherein the titanium source contains trivalent titanium.
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|---|---|---|---|
| JP25941995A JP3366163B2 (en) | 1995-09-12 | 1995-09-12 | Titanium-containing mordenite and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25941995A JP3366163B2 (en) | 1995-09-12 | 1995-09-12 | Titanium-containing mordenite and method for producing the same |
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| Publication Number | Publication Date |
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| JPH0977511A true JPH0977511A (en) | 1997-03-25 |
| JP3366163B2 JP3366163B2 (en) | 2003-01-14 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601213A (en) * | 2013-12-06 | 2014-02-26 | 天津大学 | Preparation method for low silicon-aluminum ratio nanosheet flower cluster-like mordenite molecular sieve |
| JP2017057126A (en) * | 2015-09-18 | 2017-03-23 | 国立大学法人横浜国立大学 | Manufacturing method of titanosilicate |
| CN115121047A (en) * | 2022-03-18 | 2022-09-30 | 合肥丰德科技股份有限公司 | Preparation method of modified ceramic filter element |
-
1995
- 1995-09-12 JP JP25941995A patent/JP3366163B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601213A (en) * | 2013-12-06 | 2014-02-26 | 天津大学 | Preparation method for low silicon-aluminum ratio nanosheet flower cluster-like mordenite molecular sieve |
| JP2017057126A (en) * | 2015-09-18 | 2017-03-23 | 国立大学法人横浜国立大学 | Manufacturing method of titanosilicate |
| CN115121047A (en) * | 2022-03-18 | 2022-09-30 | 合肥丰德科技股份有限公司 | Preparation method of modified ceramic filter element |
| CN115121047B (en) * | 2022-03-18 | 2024-02-02 | 合肥丰德科技股份有限公司 | Preparation method of modified ceramic filter element |
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