JP4552071B2 - Method for producing iron aluminophosphate - Google Patents

Description

【００４１】
こうしたＸ線回折ピークを持つ鉄アルミノフォスフェートには、テンプレートが含有されていても良いし、テンプレートの一部または全部が窒素焼成などの方法により除去されていても良い。
【００４２】
以上説明したように、少なくとも表１に示すＸ線回折ピークを示す鉄アルミノフォスフェートが得られるが、こうした結晶構造上の特徴を有する限りは、骨格構造内に他の元素が含まれていても良い。他の元素としては、ケイ素、リチウム、マグネシウム、チタン、ジルコニウム、バナジウム、クロム、マンガン、コバルト、ニッケル、パラジウム、銅、亜鉛、ガリウム、ゲルマニウム、砒素、スズ、カルシウム、硼素などが挙げられる。通常、他の元素が含有限度を超えて含まれる場合には、少なくとも表１に示すＸ線回折ピークを示さない。したがって、その含有限度は、上記表１のＸ線回折ピークを示すことを限度として判断され、具体的には、通常、他の元素（Ｍ）と鉄（Ｆｅ）のモル比（Ｍ／Ｆｅ）は３以下、好ましくは２以下、より好ましくは１以下、さらに好ましくは０．５以下である。
【００４３】
また、こうした結晶構造上の特徴を有する限りにおいて、この鉄アルミノフォスフェートは他のカチオンと交換可能なカチオン種を持つものものを含んでいてもよい。そうした場合のカチオンとしては、プロトン、Ｌｉ、Ｎａ、Ｋなどのアルカリ元素、Ｍｇ、Ｃａなどのアルカリ土類元素、Ｌａ，Ｃｅ等の希土類元素、Ｆｅ，Ｃｏ，Ｎｉ等の遷移金属元素などが挙げられる。中でも、プロトン、アルカリ元素、アルカリ土類元素が好ましい。
【００４４】
なお、上述した表１のＸ線回折ピークは、標準的Ｘ線粉末回折装置で測定されたＸ線回折パターンから得られたデータである。具体的な測定方法としては、ターゲットにＣｕを用い、４０ｋＶ・３０ｍＡに出力設定されたＸ線管球を線源とし、試料により回折された回折Ｘ線をモノクロメーターにてＫα線に単色化されたものを検出することにより行われる。光学条件は、発散スリット＝１°、散乱スリット＝１°、受光スリット＝０．２ｍｍで測定し、回折ピークの位置は、２θ（回折角）として表される。なお、θは、記録紙上に観察されるブラッグ角度である。オングストローム単位における面間隔（ｄ）はブラッグの条件式：２ｄｓｉｎθ＝λ、から得られる。ここで、λ＝１．５４１８４Åである。なお、ピーク位置はピークトップとして表す。強度はバックグラウンドを差し引いた後の回折ピークの高さから測定し、Ｉ／Ｉ_０×１００の値で表す。ここで、Ｉ_０は最も強いピークの強度であり、Ｉは他のピークのそれぞれにおける強度である。本発明の場合、通常Ｉ_０は、２θ＝９．５±０．３°のピークとなる。また、通常、２θの測定は、人的誤差と機械的誤差との両者を受ける。以上の誤差等を考慮して、測定値の±の範囲を約プラスマイナス０．３°として規定した。
【００４５】
（焼成後のＸ線回折パターン）
以上のように、本発明の鉄アルミノフォスフェートの製造方法について説明したが、得られた鉄アルミノフォスフェートをさらに酸素含有ガス雰囲気中で焼成した後のものの粉末Ｘ線回折測定を行った。表２は、焼成後の鉄アルミノフォスフェートの主要な回折ピークが現れる回折角（２θ）を示している。表２中の相対強度の記号は、表１と同様である。
【００４６】
【表２】

【００４７】
表２に示す焼成後の鉄アルミノフォスフェートは、上述の表１に示す鉄アルミノフォスフェートを酸素を含むガスの存在下で焼成することにより得ることができる。焼成温度は、２００℃以上８００℃以下であり、テンプレートの除去のし易さ及び／又は結晶構造の変化のし易さの観点からは３００℃以上７００℃以下が好ましく、４００℃以上６５０℃以下がより好ましい。焼成時間は、１分から１５時間であり、テンプレートの除去のし易さ及び／又は結晶構造の変化のし易さの観点からは２分から１０時間が好ましく、５分から８時間がより好ましい。なお、ここでいう焼成時間は、実質的に焼成されるものが処理温度環境中に存在する見かけの時間であり、用いる装置や試料の量により、みかけ上同じ処理時間であっても、装置内での実際の処理時間が若干異なることもある点も留意して設定される。ガス中の酸素濃度は、２ｖｏｌ％以上であり、テンプレートの除去のし易さ及び／又は結晶構造の変化のし易さの観点からは３ｖｏｌ％以上が好ましく、５ｖｏｌ％以上がより好ましい。酸素以外の含有ガスとしては、窒素、アルゴン、ヘリウムなどの不活性ガスが用いられるが、場合によっては水蒸気、窒素酸化物を体積比で１０％まで混合させてもかまわない。焼成ガスは、処理装置内を流通させてもよいし、させなくてもよいが、流通させる場合は、焼成する試料に対する重量空間速度（ＷＨＳＶ）で流通させることが好ましい。その重量空間速度（ＷＨＳＶ）としては、２０／ｈ以下、テンプレートの除去のし易さ及び／又は結晶構造の変化のし易さの観点からは１５／ｈ以下が好ましく、１０／ｈ以下がより好ましい。焼成装置としては、マッフル炉や、管状炉等の任意の加熱装置を用い、固定床、または流動床形式で行われる。
【００４８】
こうして得られた焼成後の鉄アルミノフォスフェートは、吸着材、酸反応や酸化反応用等の触媒、分離材、量子ドットや量子ワイヤーなどの光学材料、磁気材料となる半導体微粒子や蛍光体、色素などのホストとして広く用いられる。
【００４９】
【実施例】
以下、実施例により本発明を具体的に説明する。
【００５０】
（実施例１）
実施例１は、テンプレートとしてモルホリンとトリエチルアミンを使用して合成した鉄アルミノフォスフェートに関するものである。
【００５１】
水２８．０５ｇと８５％リン酸１１．５３ｇの混合物に、擬ベーマイト（２５％水含有、コンデア製）６．８ｇをゆっくりと加えて攪拌した。これをＡ液とした。Ａ液とは別に硫酸第一鉄７水和物２．７８ｇ、モルホリン５．０５ｇ、トリエチルアミン４．３５ｇ、水２９ｇを混合した液を調製した。これをＡ液にゆっくりと加えて、３時間攪拌し、以下の組成を有する出発反応物を得た。
０．２ＦｅＳＯ_４：Ａｌ_２Ｏ_３：Ｐ_２Ｏ_５：１．１６モルホリン：０．８６トリエチルアミン：７０Ｈ_２Ｏ
【００５２】
上記の出発反応物をテフロン（登録商標）内筒の入った２００ｃｃのステンレス製オートクレーブに仕込み、静置状態で１６０℃で４日間反応させた。反応後冷却して、デカンテーションにより上澄みを除いて、沈殿物を回収した。その沈殿物を水で３回洗浄した後濾別し、１２０℃で乾燥した。こうして得られた鉄アルミノフォスフェートの粉末ＸＲＤの結果は以下の表３の通りであった。図１には、そのＸＲＤパターンを示す。
【００５３】
【表３】

【００５４】
得られた鉄アルミノフォスフェートを塩酸水溶液で加熱溶解させ、ＩＣＰ分析により元素分析を行ったところ、骨格構造のアルミニウムとリンと鉄の合計に対する各成分の構成割合（モル比）は、鉄が１３．８％、アルミニウムが３７．４％、リンが４８．８％であった。
【００５５】
なお、その後、テンプレートが含まれた上記鉄アルミノフォスフェートから３ｇを採取し、縦型の石英焼成管に入れ、１００ｍｌ／分の空気気流下、１℃／分で５５０℃まで昇温し、そのまま５５０℃で６時間焼成を行った。こうして得られた焼成後の鉄アルミノフォスフェートのＸＲＤを測定したところ、以下の表の通りであった。図２は、その焼成品のＸＲＤパターンである。
【００５６】
【表４】

【００５７】
また、上記鉄アルミノフォスフェートを、空気気流中ではなく窒素雰囲気中で焼成した後のもののＸＲＤ結果を表５に示した。
【００５８】
【表５】

【００５９】
また、表５に示した窒素焼成サンプルを、空気により再焼成した後のもののＸＲＤ結果を表６に示した。これは表４と同じになった。
【００６０】
【表６】

【００６１】
（実施例２）
実施例２は、テンプレートとしてモルホリンを単独で使用して製造した鉄アルミノフォスフェートに関するものである。
【００６２】
水２１０ｇに８５％リン酸８６．５ｇを加え、これに擬ベーマイト（２５％水含有、コンデア製）５１ｇをゆっくりと加え、３時間攪拌した。これに、硫酸第一鉄７水和物４１．７ｇを水２１８ｇに溶かした液を加え、さらにモルホリン７５．７ｇをゆっくりと加えてさらに３時間攪拌した。そして以下の組成を有するゲル状の出発反応物を得た。
０．４ＦｅＳＯ_４：Ａｌ_２Ｏ_３：Ｐ_２Ｏ_５：２モルホリン：７０Ｈ_２Ｏ
【００６３】
こうして得られた混合物をテフロン（登録商標）内筒の入った１リットルのステンレス製オートクレーブに仕込み、１００ｒｐｍで攪拌しながら１８０℃で２４時間反応させた。反応後冷却して、デカンテーションにより上澄みを除いて沈殿物を回収した。沈殿物を水で３回洗浄した後濾別し、１２０℃で乾燥した。表７は、こうして得られた鉄アルミノフォスフェートのＸＲＤ測定結果である。
【００６４】
【表７】

【００６５】
このサンプルを実施例１と同じ方法でＩＣＰ分析により元素分析を行った。その結果、アルミニウムとリンと鉄の合計に対する各成分の構成割合（モル比）は、鉄が１７．２％、アルミニウムが２９．４％、リンが５３．４％であった。
【００６６】
（実施例３）
実施例３は、テンプレートとしてモルホリンとトリエチルアミンを使用して製造した鉄アルミノフォスフェートに関するものである。
【００６７】
水２８．０５ｇに８５％リン酸１１．５ｇを加え、これに擬ベーマイト（２５％水含有、コンデア製）６．８ｇをゆっくりと加え、３時間攪拌した。これに、硫酸第一鉄７水和物８．３ｇを水２９ｇに溶かした液を加え、さらにモルホリン５．０５ｇとトリエチルアミン４．３５ｇを混合した液をゆっくりと加えてさらに３時間攪拌した。そして以下の組成を有するゲル状の出発反応物を得た。
０．６ＦｅＳＯ_４：Ａｌ_２Ｏ_３：Ｐ_２Ｏ_５：１．１６モルホリン：０．８６トリエチルアミン：７０Ｈ_２Ｏ
【００６８】
こうして得られた混合物をテフロン（登録商標）内筒の入った０．２リットルのステンレス製オートクレーブに仕込み、静置状態で１６０℃で４日間反応させた。反応後冷却して、デカンテーションにより上澄みを除いて沈殿物を回収した。沈殿物を水で３回洗浄した後濾別し、１２０℃で乾燥した。表８は、得られた鉄アルミノフォスフェートのＸＲＤ測定結果である。
【００６９】
【表８】

【００７０】
このサンプルを実施例１と同じ方法でＩＣＰ分析により元素分析を行った。その結果、アルミニウムとリンと鉄の合計に対する各成分の構成割合（モル比）は、鉄が１３．２％、アルミニウムが３８．３％、リンが４８．５％であった。
【００７１】
（実施例４）
実施例４は、テンプレートとしてモルホリンとトリエチルアミンを使用して製造した鉄アルミノフォスフェートに関するものである。
【００７２】
水２６ｇに８５％リン酸１１．５ｇを加え、これに擬ベーマイト（２５％水含有、コンデア製）５．４４ｇをゆっくりと加え、２時間攪拌した。これに、硫酸第一鉄７水和物８．３ｇを水２６ｇに溶かした液を加え、さらにモルホリン２．１８ｇとシクロヘキシルアミン７．４３ｇを混合した液をゆっくりと加えてさらに２時間攪拌した。そして以下の組成を有するゲル状の出発反応物を得た。
０．６ＦｅＳＯ_４：０．８Ａｌ_２Ｏ_３：Ｐ_２Ｏ_５：０．５モルホリン：１．５シクロヘキシルアミン：６０Ｈ_２Ｏ
【００７３】
得られた混合物をテフロン（登録商標）内筒の入った０．２ｌのステンレス製オートクレーブに仕込み、静置状態で１9０℃で1日間反応させた。反応後冷却して、デカンテーションにより上澄みを除いて沈殿物を回収した。沈殿物を水で３回洗浄した後濾別し、１２０℃で乾燥した。表９は、得られた鉄アルミノフォスフェートのＸＲＤ測定結果である。
【００７４】
【表９】

【００７５】
このサンプルを実施例１と同じ方法でＩＣＰ分析により元素分析を行った。その結果、アルミニウムとリンと鉄の合計に対する各成分の構成割合（モル比）は、鉄が１４．１％、アルミニウムが３８．４％、リンが４７．４％であった。
【００７６】
（実施例５）
実施例５は、テンプレートとしてモルホリンとトリエチルアミンを使用して合成した、Ｓｉ含有鉄アルミノフォスフェートに関するものである。
【００７７】
水２８．０５ｇに８５％リン酸１１．５ｇを加え、これに擬ベーマイト（２５％水含有、コンデア製）６．８ｇをゆっくりと加え、３時間攪拌した。これに、硫酸第一鉄７水和物２．７８ｇを水２９ｇに溶かし、それにｆｕｍｅｄシリカ（アエロジル２００）０．１５ｇを加えた液を加え、さらにモルホリン５．０５ｇとトリエチルアミン４．３５ｇを混合した液をゆっくりと加えてさらに３時間攪拌した。そして以下の組成を有するゲル状の出発反応物を得た。
０．２ＦｅＳＯ_４：０．０５ＳｉＯ_２：Ａｌ_２Ｏ_３：Ｐ_２Ｏ_５：１．１６モルホリン：０．８６トリエチルアミン：７０Ｈ_２Ｏ
【００７８】
得られた混合物をテフロン（登録商標）内筒の入った０．２ｌのステンレス製オートクレーブに仕込み、静置状態で１７０℃で２日間反応させた。反応後冷却して、デカンテーションにより上澄みを除いて沈殿物を回収した。沈殿物を水で３回洗浄した後濾別し、１２０℃で乾燥した。表１０は、こうして得られた鉄アルミノフォスフェートのＸＲＤ測定結果である。
【００７９】
【表１０】

【００８０】
このサンプルを実施例１と同じ方法でＩＣＰ分析により元素分析を行った。その結果、アルミニウムとリンと鉄とケイ素の合計に対する各成分の構成割合（モル比）は、鉄が９．９％、ケイ素が２．８％、アルミニウムが４０．７％、リンが４６．７％であった。
【００８１】
（実施例６）
実施例６は、テンプレートとしてジイソプロピルエチルアミンとメチルブチルアミンを用いて合成した、鉄アルミノフォスフェートである。
【００８２】
水１５ｇに８５％リン酸８．０７ｇを加え、これに擬ベーマイト（２５％水含有、コンデア製）３．８ｇをゆっくりと加え、３時間攪拌した。これに、硫酸第一鉄７水和物３．８８ｇを水２０ｇに溶かした液を加え、さらにジイソプロピルエチルアミン４．５５ｇとメチルブチルアミン３．０５ｇを混合した液をゆっくりと加えてさらに３時間攪拌した。そして以下の組成を有するゲル状の出発反応物を得た。
０．４ＦｅＳＯ_４：０．８Ａｌ_２Ｏ_３：Ｐ_２Ｏ_５：１ジイソプロピルエチルアミン：１メチルブチルアミン：６０Ｈ_２Ｏ
【００８３】
こうして得られた混合物をテフロン（登録商標）内筒の入った０．２ｌのステンレス製オートクレーブに仕込み、静置状態で１７０℃で２日間反応させた。反応後冷却して、デカンテーションにより上澄みを除いて沈殿物を回収した。沈殿物を水で３回洗浄した後濾別し、１２０℃で乾燥した。表１１は、こうして得られた鉄アルミノフォスフェートのＸＲＤ測定結果である。
【００８４】
【表１１】

【００８５】
このサンプルを実施例１と同じ方法でＩＣＰ分析により元素分析を行った。その結果、アルミニウムとリンと鉄の合計に対する各成分の構成割合（モル比）は、鉄が９．２％、アルミニウムが４２．６％、リンが４８．２％であった。
【００８６】
（実施例７）
実施例７は、テンプレートとしてモルホリンとトリエチルアミンをテンプレートとして合成したＳｉ含有のＣＨＡ型の鉄アルミノフォスフェートである。
【００８７】
水２８．０５ｇに８５％リン酸１１．５ｇを加え、これに擬ベーマイト（２５％水含有、コンデア製）６．８ｇをゆっくりと加え、３時間攪拌した。これに、硫酸第一鉄７水和物１．４ｇを水２９ｇに溶かし、それにｆｕｍｅｄシリカ（アエロジル２００）０．３ｇを加えた液を加え、さらにモルホリン５．０５ｇとトリエチルアミン４．３５ｇを混合した液をゆっくりと加えてさらに３時間攪拌した。そして以下の組成を有するゲル状の出発反応物を得た。
０．１ＦｅＳＯ_４：０．１ＳｉＯ_２：Ａｌ_２Ｏ_３：Ｐ_２Ｏ_５：１．１６モルホリン：０．８６トリエチルアミン：７０Ｈ_２Ｏ
【００８８】
得られた混合物をテフロン（登録商標）内筒の入った０．２ｌのステンレス製オートクレーブに仕込み、静置状態で１６０℃で３日間反応させた。反応後冷却して、デカンテーションにより上澄みを除いて沈殿物を回収した。沈殿物を水で３回洗浄した後濾別し、１２０℃で乾燥した。表１２は、こうして得られた鉄アルミノフォスフェートのＸＲＤ測定結果である。
【００８９】
【表１２】

【００９０】
このサンプルを実施例１と同じ方法でＩＣＰ分析により元素分析を行った。その結果、アルミニウムとリンと鉄の合計に対する各成分の構成割合（モル比）は、鉄が６．６％、ケイ素が４．６％、アルミニウムが４３．６％、リンが４３．６％であった。
【００９１】
（比較例）
ＵＳＰ４５５４１４３に記載されている実施例１０にしたがって合成した。
【００９２】
水３２ｇに８５％リン酸１１．６ｇを加え、これにアルキニウムイソプロポキソド１６．４ｇをゆっくりと加え、３時間攪拌した。これに、硫酸第一鉄７水和物５．６ｇを加え、さらに３５ｗｔ％テトラエチルアンモニウムヒドロキシド（ＴＥＡＯＨ）水溶液４２．１ｇを混合した液を加えてさらに３時間攪拌した。そして以下の組成を有するゲル状の出発反応物を得た。
０．４ＦｅＳＯ_４：０．８Ａｌ_２Ｏ_３：Ｐ_２Ｏ_５：２．０ＴＥＡＯＨ：６８Ｈ_２Ｏ
【００９３】
得られた混合物をテフロン（登録商標）内筒の入った０．２ｌのステンレス製オートクレーブに仕込み、静置状態で２００℃で４２時間反応させた。反応後冷却して、遠心分離機により沈殿物を回収した。沈殿物を水で洗浄、濾別し、１２０℃で乾燥した。こうしてできたテンプレート入りのゼオライトを実施例１と同様に５５０℃空気気流下６時間の焼成を行い、焼成品を得た。
【００９４】
テンプレート入り（テンプレート未除去品）のＸＲＤ図を図３に、焼成後のＸＲＤ図を図４に示す。図３のＸＲＤ強度は、実施例１の図１に比べて小さく、結晶性が不十分である可能性がある。また、焼成後の図４には、実施例１の焼成後の図２には見られない、２５°（２θ）付近のアモルファス由来のブロードピークがはっきりとあらわれ、また２０°（２θ）付近にはデンス成分と考えられる不純物成分があらわれており、焼成により構造が大きく破壊されている事がわかる。
【００９５】
【発明の効果】
以上説明したように、本発明の鉄アルミノフォスフェートの製造方法によれば、窒素を含む脂環式複素環化合物、シクロアルキル基を有するアミンおよびアルキル基を有するアミンから選択されるテンプレートは、入手しやすく安価であり安全性に優れているので、工業生産にとって極めて好ましい。さらに、製造された鉄アルミノフォスフェートの取り扱いも容易で構造破壊も起きにくいという、従来にない格別の効果がある。
【図面の簡単な説明】
【図１】本発明により製造された鉄アルミノフォスフェートの典型的なＸ線回折パターンの一例である。
【図２】実施例１の焼成品のＸ線回折パターンである。
【図３】比較例テンプレート未除去品のＸ線回折パターンである。
【図４】比較例の焼成品のＸ線回折パターンである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing iron aluminophosphate.
[0002]
[Background Art and Problems to be Solved by the Invention]
Zeolite includes crystalline silicates, crystalline aluminophosphates, and the like as defined by the International Zeolite Association (IZA). Among these zeolites, in particular, a method for producing iron aluminophosphate using iron as a heteroatom is described in the example of US Pat. No. 4,554,143.
[0003]
However, the iron aluminophosphate production method uses an expensive tetraethylammonium salt as a template, and improvement in production cost has been demanded.
[0004]
In addition, when hydrothermal synthesis is performed using the tetraethylammonium salt as a template, there is a problem that fine particles are generated and handling such as filtration is poor, and further, the structure is obtained when the template is removed by firing. There is a problem that it is fragile. This is an obstacle to industrial production of iron aluminophosphate.
[0005]
The present invention has been made to solve the above problems, and its purpose is to use an iron aluminophosphate that can be used with a cheaper template, is easy to handle, and is not destroyed by firing or the like. It is to provide a manufacturing method.
[0006]
[Means for Solving the Problems]
  The method for producing an iron aluminophosphate of the present invention that solves the above problems comprises mixing an iron source, an aluminum source, a phosphorus source, and a template.didA method for producing iron aluminophosphate by later hydrothermal synthesis, wherein the template comprises a nitrogen-containing alicyclic heterocyclic compound, an amine having a cycloalkyl group and an amine having an alkyl groupIn the powder X-ray diffraction measurement with Cu-Kα ray having an X-ray wavelength of 1.5418 mm, the iron aluminophosphate is used at least in the powder X-ray diffraction measurement using at least one compound selected from two or more groups. Diffraction angles of 5 ± 0.3, 13.0 ± 0.3, 16.0 ± 0.3, 20.7 ± 0.3, 26.0 ± 0.3 and 30.8 ± 0.4 (2θ ) Shows a diffraction peakIt has a special feature.
[0007]
According to the present invention, as a template, an alicyclic heterocyclic compound containing nitrogen, an amine having a cycloalkyl group and an amine having an alkyl group are selected and used, so that they are easily available and inexpensive. The iron aluminophosphate thus produced is easy to handle and structural destruction is less likely to occur.
[0008]
  ironThe aluminophosphate can be exemplified by AEI, AFX, GIS, CHA, VFI, AFS, LTA, FAU, AFU, etc., when it is shown by a code that determines the structure of the zeolite according to International Zeolite Association (IZA).However, the iron aluminophosphate is, CHA in the codeInBelongRumoIs.
[0010]
Further, in the above-described method for producing an iron aluminophosphate of the present invention, when the mixing ratio of the iron source, the aluminum source and the phosphorus source is expressed by the molar ratio of the oxide, FeO / Al₂O₃Is 1.0 or less and P₂O₅ / Al₂O₃The characteristic is that the value of is 0.6 or more.
[0011]
According to this invention, FeO / Al₂O₃Is 1.0 or less and P₂O₅ / Al₂O₃Since the value of is 0.6 or more, Fe is efficiently introduced into the skeleton structure.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The method for producing the iron aluminophosphate of the present invention will be described in detail below.
[0013]
(Constituent raw materials)
Iron aluminophosphate (hereinafter, also referred to as FAPO) is used as an aluminum source, an iron source, a phosphorus source, and a template raw material, and after mixing them, is produced by hydrothermal synthesis.
[0014]
Aluminum source: The aluminum source is not particularly limited. Usually, aluminum alkoxide such as pseudoboehmite, aluminum isopropoxide, aluminum triethoxide, aluminum hydroxide, alumina sol, sodium aluminate, etc. are used. Among these, pseudoboehmite is preferable from the viewpoint of easy handling and reactivity.
[0015]
Iron source: The iron source is also not particularly limited, and is usually an inorganic acid iron such as iron sulfate, iron nitrate, iron phosphate, iron chloride or iron bromide, or an organic acid iron such as iron acetate, iron oxalate or iron citrate. Iron organometallic compounds such as iron pentacarbonyl and ferrocene are used. Among these, from the viewpoint of solubility in water, inorganic acid iron and organic acid iron are preferable, and among them, divalent iron compounds such as ferrous sulfate are more preferable. In some cases, colloidal iron hydroxide may be used.
[0016]
Phosphorus source: The phosphorus source is usually phosphoric acid, but aluminum phosphate may be used.
[0017]
Other elements: As long as it finally has a powder X-ray diffraction pattern consisting of at least the X-ray diffraction peaks shown in Table 1, other elements may be contained in the skeleton structure. Examples of other elements include silicon, lithium, magnesium, titanium, zirconium, vanadium, chromium, manganese, cobalt, nickel, palladium, copper, zinc, gallium, germanium, arsenic, tin, calcium, and boron.
[0018]
Template: The following amines are used as a template. Examples of amines include (1) an alicyclic heterocyclic compound containing nitrogen as a hetero atom, (2) an amine having a cycloalkyl group, and (3) an amine having an alkyl group. These may be used singly, but when a quaternary ammonium salt is used alone, it is likely to have poor crystallinity, so at least one of the three groups of amines is selected from each group. It is preferable to select and use one or more compounds for each.
[0019]
Here, each of the above amines will be described in more detail.
[0020]
First, an alicyclic heterocyclic compound containing nitrogen as a hetero atom will be described.
The alicyclic heterocyclic compound containing nitrogen as a hetero atom is usually a 5- to 7-membered ring, preferably a 6-membered ring. The number of heteroatoms contained in the heterocycle is usually 3 or less, preferably 2 or less. The type of hetero atom is not particularly limited except nitrogen, but from the viewpoint of ease of synthesis, a hetero atom containing oxygen is preferable. The positions of the heteroatoms are not particularly limited, but those in which the heteroatoms are not adjacent to each other are preferable from the viewpoint of ease of synthesis. The molecular weight is 250 or less, preferably 200 or less, more preferably 150 or less from the viewpoint of ease of synthesis.
[0021]
Examples of such alicyclic heterocyclic compounds containing nitrogen as a heteroatom include morpholine, N-methylmorpholine, piperidine, piperazine, N, N′-dimethylpiperazine, 1,4-diazabicyclo (2,2,2) octane. , N-methylpiperidine, 3-methylpiperidine, quinuclidine, pyrrolidine, N-methylpyrrolidone, hexamethyleneimine and the like. Of these, morpholine, hexamethyleneimine, and piperidine are preferable from the viewpoint of ease of synthesis, and morpholine is particularly preferable.
[0022]
Next, an amine having a cycloalkyl group will be described. In the amine having a cycloalkyl group, the number of the cycloalkyl group is preferably 2 or less, more preferably 1 per amine molecule. Moreover, carbon number of a cycloalkyl group is 5-7 normally, Preferably it is 6. The number of cycloalkyl cyclo rings is not particularly limited, but is usually preferably 1. Moreover, it is preferable from the point of easiness of a synthesis | combination that the cycloalkyl group has couple | bonded with the nitrogen atom of the amine compound. The molecular weight is 250 or less, preferably 200 or less, more preferably 150 or less from the viewpoint of ease of synthesis.
[0023]
Examples of the amine having such a cycloalkyl group include cyclohexylamine, dicyclohexylamine, N-methylcyclohexylamine, N, N-dimethylcyclohexylamine, and cyclopentylamine, and cyclohexylamine is particularly preferable.
[0024]
Next, the amine having an alkyl group will be described. In the amine having an alkyl group, any number of the alkyl groups may be contained in one amine molecule, but 3 is preferred. The number of carbon atoms of the alkyl group is preferably 4 or less, and the total number of carbon atoms of all alkyl groups in one molecule is more preferably 10 or less. The molecular weight is 250 or less, preferably 200 or less, more preferably 150 or less from the viewpoint of ease of synthesis.
[0025]
Examples of amines having such alkyl groups include di-n-propylamine, tri-n-propylamine, tri-isopropylamine, triethylamine, triethanolamine, N, N-diethylethanolamine, N, N-dimethylethanol. Amine, N-methyldiethanolamine, N-methylethanolamine, di-n-butylamine, neopentylamine, di-n-pentylamine, isopropylamine, t-butylamine, ethylenediamine, di-isopropyl-ethylamine, N-methyl-n -Butylamine and the like, di-n-propylamine, tri-n-propylamine, tri-isopropylamine, triethylamine, di-n-butylamine, isopropylamine, t-butylamine, ethylenediamine, di-isopropyl Le - ethylamine, preferably in that N- methyl -n- butylamine synthetic ease, triethylamine is particularly preferred.
[0026]
Each of these amines can be used as a template source by combining one or two or more thereof, and used as a raw material for hydrothermal synthesis. When one of these is used, (1) morpholine in an alicyclic heterocyclic compound containing nitrogen as a hetero atom, or (2) cyclohexylamine in an amine having a cycloalkyl group is preferable. Of these, morpholine is particularly preferred.
[0027]
Among these, as a preferable combination, a template includes (1) an alicyclic heterocyclic compound containing nitrogen as a hetero atom, (2) an amine having a cycloalkyl group, and (3) an amine having an alkyl group. It is preferable to use one or more compounds from two or more groups. By combining in this way, there is an advantage / effect that it is easy to synthesize FAPO having a desired element ratio or highly crystalline FAPO. Among these, (1) in the case of a combination of two or more containing an alicyclic heterocyclic compound containing nitrogen as a heteroatom, from the viewpoint of easy synthesis of FAPO with a desired element ratio or highly crystalline FAPO, more preferable. As a specific preferred combination, a combination of two or more of morpholine, triethylamine and cyclohexylamine, more preferably a combination of two or more containing morpholine is more preferable. Although the mixing ratio of each group of these templates needs to be selected in a timely manner according to conditions, the molar ratio of the two types of templates to be mixed is in the range of 1:20 to 20: 1. From the viewpoint of ease of synthesis of highly crystalline FAPO, 1:10 to 10: 1 is preferable, and 1: 5 to 5: 1 is more preferable. Although other templates may be contained, in that case, the molar ratio is usually 20% or less, preferably 10% or less. These templates are advantageous in that they are inexpensive and easy to handle and less corrosive than conventional ones (for example, tetraethylammonium hydroxide).
[0028]
In the method for producing iron aluminophosphate of the present invention, the crystallization rate of iron aluminophosphate can be improved by combining each template and reacting under preferable reaction conditions. An iron aluminophosphate can be easily produced, an iron aluminophosphate having a stable structure that is hard to break can be produced, and advantageous effects such as suppression of impurity generation can be obtained. However, when a single type of template is used, it is slightly inferior to a template obtained by mixing a plurality of templates in terms of a wide range of reaction conditions, a high yield of a desired zeolite, a fast crystallization rate, and the like. Therefore, in the production of the iron aluminophosphate of the present invention, a template in which a plurality of types of compounds selected from the above-mentioned (1) to (3) are combined is preferably used, and the template exhibits a single action due to the synergistic action exhibited by these templates. There is an advantage that an effect that cannot be obtained by a template can be obtained.
[0029]
(Hydrothermal synthesis)
Next, hydrothermal synthesis in the method for producing iron aluminophosphate will be described.
[0030]
First, an aqueous gel is prepared by mixing an iron source, an aluminum source, a phosphoric acid source, a template and water. The mixing order is not limited and may be appropriately selected depending on the conditions to be used. Usually, however, first a phosphoric acid source and an aluminum source are mixed with water, and then an iron source and a template are mixed therewith.
[0031]
The composition of the aqueous gel affects the ease of synthesis of the desired one. When the aluminum source, the iron source and the phosphate source are expressed in terms of the molar ratio of the oxide, FeO / Al₂O₃The value of is usually greater than 0 and 1.0 or less, preferably 0.9 or less, and more preferably 0.8 or less.
[0032]
P₂O₅ / Al₂O₃The ratio affects the ease of synthesis of the desired product, and is usually 0.6 or more, preferably 0.8 or more, more preferably 1 or more, usually 1.8 or less, preferably 1.7 or less, Preferably it is 1.6 or less.
[0033]
The total amount of templates affects the ease of synthesis and economics of what is desired.₂O₅The molar ratio of the template to is usually 0.2 or more, preferably 0.5 or more, more preferably 1 or more, and usually 4 or less, preferably 3 or less, more preferably 2.5 or less. In addition, the mixing ratio of two or more types of templates affects the ease of synthesis of the desired one and needs to be appropriately selected according to the conditions. For example, when morpholine and triethylamine are used as described above, The molar ratio of morpholine / triethylamine is 0.05 to 20, preferably 0.1 to 10, and more preferably 0.2 to 9. The order of mixing one or more templates selected from each of the two or more groups is not particularly limited, and after preparing the template, it may be mixed with other substances, and each template may be mixed with other substances. May be mixed with.
[0034]
In addition, the proportion of water affects the ease of synthesis and economics of the desired product, and Al₂O₃The molar ratio is usually 3 or more, preferably 5 or more, more preferably 10 or more, and is usually 200 or less, preferably 150 or less, more preferably 120 or less. The pH of the aqueous gel affects the ease of synthesis of the desired gel, and is usually 4 or more, preferably 4.5 or more, more preferably 5 or more, and usually 10 or less, preferably 9 or less, more preferably 8 or less. It is.
[0035]
In the aqueous gel, components other than those described above may coexist if desired. As an advantage of coexistence, there is a possibility that a new effect can be obtained. Examples of such components include hydrophilic organic solvents such as hydroxides and salts of alkali metals and alkaline earth metals, and alcohols. The ratio of coexistence affects the ease of synthesis of the desired product, and in the case of alkali metal or alkaline earth metal hydroxides or salts, Al₂O₃The molar ratio is usually 0.2 or less, preferably 0.1 or less. In the case of a hydrophilic organic solvent such as alcohol, the molar ratio to water is usually 0.5 or less, preferably 0.3. It is as follows.
[0036]
Under such conditions, hydrothermal synthesis is performed by placing the aqueous gel in a pressure-resistant container and maintaining a predetermined temperature under stirring or standing under self-generated pressure or gas pressure that does not inhibit crystallization.
[0037]
The reaction temperature of hydrothermal synthesis affects the ease of synthesis of the desired product, and is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and usually 300 ° C. or lower, preferably 250 ° C. or lower. More preferably, it is 220 ° C. or lower. The reaction time affects the ease of synthesis of the desired product, and is usually 2 hours or more, preferably 3 hours or more, more preferably 5 hours or more, and usually 30 days or less, preferably 10 days or less, more preferably 4 days or less. The reaction temperature may be constant during the reaction or may be changed stepwise.
[0038]
After the hydrothermal synthesis, the product is separated. The method for separating the product is not particularly limited. Usually, it is separated by filtration, decantation, etc., washed with water, and dried at a temperature of room temperature to 150 ° C. or lower to obtain a zeolite containing the product template. The iron aluminophosphate obtained by the production method of the present invention is industrially preferable because it has excellent crystallinity and is difficult to break, and therefore can be easily subjected to treatment such as separation filtration.
[0039]
(Crystal structure)
By separating after the hydrothermal synthesis described above, an iron aluminophosphate showing a powder X-ray diffraction pattern having at least the X-ray diffraction peaks shown in Table 1 is obtained. A typical powder X-ray diffraction pattern (see Example 1) obtained at this time is shown in FIG. The iron aluminophosphate was calcined in the presence of an inert gas such as nitrogen, and a part or all of the template was removed to obtain a powder X-ray diffraction pattern having at least the X-ray diffraction peaks shown in Table 1. An iron aluminophosphate having the following formula is obtained. In addition, since powder X-ray diffraction measurement is normally performed in air, the sample used for the measurement here is rehydrated in atmospheric air. The relative strengths in Table 1 are indicated by the symbols vs, s, m, w, and vw, which correspond to extremely strong, strong, moderate, weak, and extremely weak, respectively.
[0040]
[Table 1]

[0041]
The iron aluminophosphate having such an X-ray diffraction peak may contain a template, or a part or all of the template may be removed by a method such as nitrogen firing.
[0042]
As described above, an iron aluminophosphate having at least the X-ray diffraction peaks shown in Table 1 can be obtained. However, as long as it has such a crystal structure feature, other elements are included in the skeleton structure. good. Examples of other elements include silicon, lithium, magnesium, titanium, zirconium, vanadium, chromium, manganese, cobalt, nickel, palladium, copper, zinc, gallium, germanium, arsenic, tin, calcium, and boron. Usually, when other elements are contained exceeding the content limit, at least the X-ray diffraction peaks shown in Table 1 are not shown. Therefore, the content limit is determined on the basis of showing the X-ray diffraction peak of Table 1 above. Specifically, the molar ratio of other elements (M) and iron (Fe) (M / Fe) is usually used. Is 3 or less, preferably 2 or less, more preferably 1 or less, and still more preferably 0.5 or less.
[0043]
Moreover, as long as it has such a crystal structural feature, the iron aluminophosphate may include those having a cation species exchangeable with other cations. Examples of cations in such cases include protons, alkaline elements such as Li, Na, and K, alkaline earth elements such as Mg and Ca, rare earth elements such as La and Ce, and transition metal elements such as Fe, Co, and Ni. It is done. Among these, protons, alkali elements, and alkaline earth elements are preferable.
[0044]
The X-ray diffraction peaks in Table 1 described above are data obtained from an X-ray diffraction pattern measured with a standard X-ray powder diffractometer. As a specific measurement method, Cu is used as a target, an X-ray tube set to output at 40 kV and 30 mA is used as a radiation source, and the diffracted X-ray diffracted by the sample is monochromatized into Kα rays by a monochromator. This is done by detecting the object. Optical conditions were measured with a divergence slit = 1 °, a scattering slit = 1 °, and a light receiving slit = 0.2 mm, and the position of the diffraction peak is expressed as 2θ (diffraction angle). Is the Bragg angle observed on the recording paper. The surface separation (d) in angstrom units is obtained from Bragg's conditional expression: 2 dsin θ = λ. Here, λ = 1.54184Å. The peak position is expressed as a peak top. The intensity is measured from the height of the diffraction peak after subtracting the background, and the I / I₀It represents with the value of x100. Where I₀Is the intensity of the strongest peak, and I is the intensity at each of the other peaks. In the case of the present invention, usually I₀Has a peak at 2θ = 9.5 ± 0.3 °. In general, the measurement of 2θ is subject to both human error and mechanical error. In consideration of the above errors and the like, the range of ± of the measured value is defined as about plus or minus 0.3 °.
[0045]
(X-ray diffraction pattern after firing)
As mentioned above, although the manufacturing method of the iron aluminophosphate of this invention was demonstrated, the powder X-ray-diffraction measurement of the thing after baking the obtained iron aluminophosphate in oxygen-containing gas atmosphere was performed. Table 2 shows the diffraction angle (2θ) at which the main diffraction peak of the iron aluminophosphate after firing appears. The relative intensity symbols in Table 2 are the same as in Table 1.
[0046]
[Table 2]

[0047]
The iron aluminophosphate after firing shown in Table 2 can be obtained by firing the iron aluminophosphate shown in Table 1 in the presence of a gas containing oxygen. The firing temperature is 200 ° C. or higher and 800 ° C. or lower, and is preferably 300 ° C. or higher and 700 ° C. or lower, and preferably 400 ° C. or higher and 650 ° C. or lower from the viewpoint of ease of template removal and / or change in crystal structure. Is more preferable. The firing time is from 1 minute to 15 hours, and preferably from 2 minutes to 10 hours, more preferably from 5 minutes to 8 hours, from the viewpoint of ease of template removal and / or ease of change of crystal structure. Note that the firing time here is the apparent time that the material that is fired is present in the processing temperature environment. Depending on the amount of equipment and sample used, It is also set with attention that the actual processing time may be slightly different. The oxygen concentration in the gas is 2 vol% or more, preferably 3 vol% or more, and more preferably 5 vol% or more from the viewpoint of ease of template removal and / or ease of change of crystal structure. As the gas other than oxygen, an inert gas such as nitrogen, argon, or helium is used. However, depending on the case, water vapor or nitrogen oxide may be mixed up to 10% by volume. The firing gas may or may not be circulated in the processing apparatus, but when circulated, it is preferably circulated at a weight space velocity (WHSV) with respect to the sample to be fired. The weight space velocity (WHSV) is 20 / h or less, preferably 15 / h or less, and more preferably 10 / h or less from the viewpoint of ease of template removal and / or easy change of crystal structure. preferable. As a baking apparatus, arbitrary heating apparatuses, such as a muffle furnace and a tubular furnace, are used, and it is performed by a fixed bed or a fluidized bed form.
[0048]
The thus-baked iron aluminophosphate is composed of an adsorbent, a catalyst for acid reaction and oxidation reaction, a separating material, an optical material such as quantum dots and quantum wires, and semiconductor fine particles, phosphors and dyes that become magnetic materials. Widely used as a host.
[0049]
【Example】
Hereinafter, the present invention will be described specifically by way of examples.
[0050]
Example 1
Example 1 relates to an iron aluminophosphate synthesized using morpholine and triethylamine as templates.
[0051]
To a mixture of 28.05 g of water and 11.53 g of 85% phosphoric acid, 6.8 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added and stirred. This was designated as liquid A. Separately from liquid A, a liquid in which 2.78 g of ferrous sulfate heptahydrate, 5.05 g of morpholine, 4.35 g of triethylamine, and 29 g of water were prepared. This was slowly added to the liquid A and stirred for 3 hours to obtain a starting reaction product having the following composition.
0.2FeSO₄: Al₂O₃: P₂O₅: 1.16 morpholine: 0.86 triethylamine: 70H₂O
[0052]
The above starting reaction product was charged into a 200 cc stainless steel autoclave containing a Teflon (registered trademark) inner cylinder and allowed to react at 160 ° C. for 4 days in a stationary state. After the reaction, the reaction mixture was cooled, the supernatant was removed by decantation, and the precipitate was collected. The precipitate was washed three times with water, filtered off and dried at 120 ° C. The results of the iron aluminophosphate powder XRD thus obtained were as shown in Table 3 below. FIG. 1 shows the XRD pattern.
[0053]
[Table 3]

[0054]
The obtained iron aluminophosphate was heated and dissolved in an aqueous hydrochloric acid solution and subjected to elemental analysis by ICP analysis. As a result, the composition ratio (molar ratio) of each component to the total of aluminum, phosphorus and iron in the skeleton structure was 13 for iron. 0.8%, aluminum 37.4% and phosphorus 48.8%.
[0055]
After that, 3 g was collected from the iron aluminophosphate containing the template, put into a vertical quartz fired tube, heated to 550 ° C. at 1 ° C./min in an air stream of 100 ml / min, and left as it was. Firing was performed at 550 ° C. for 6 hours. When the XRD of the iron aluminophosphate after firing thus obtained was measured, it was as shown in the following table. FIG. 2 is an XRD pattern of the fired product.
[0056]
[Table 4]

[0057]
Table 5 shows the XRD results of the iron aluminophosphate after firing in a nitrogen atmosphere rather than in an air stream.
[0058]
[Table 5]

[0059]
Table 6 shows the XRD results of the nitrogen fired samples shown in Table 5 after refired with air. This is the same as Table 4.
[0060]
[Table 6]

[0061]
(Example 2)
Example 2 relates to an iron aluminophosphate produced using morpholine alone as a template.
[0062]
To 210 g of water, 86.5 g of 85% phosphoric acid was added, and 51 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added thereto and stirred for 3 hours. To this was added a solution obtained by dissolving 41.7 g of ferrous sulfate heptahydrate in 218 g of water, and 75.7 g of morpholine was slowly added thereto, followed by further stirring for 3 hours. A gel-like starting reaction product having the following composition was obtained.
0.4FeSO₄: Al₂O₃: P₂O₅: 2 morpholine: 70H₂O
[0063]
The mixture thus obtained was charged into a 1 liter stainless steel autoclave containing a Teflon (registered trademark) inner cylinder and reacted at 180 ° C. for 24 hours while stirring at 100 rpm. After the reaction, the reaction mixture was cooled and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed with water three times, filtered off and dried at 120 ° C. Table 7 shows XRD measurement results of the iron aluminophosphate thus obtained.
[0064]
[Table 7]

[0065]
This sample was subjected to elemental analysis by ICP analysis in the same manner as in Example 1. As a result, the constituent ratio (molar ratio) of each component with respect to the total of aluminum, phosphorus, and iron was 17.2% for iron, 29.4% for aluminum, and 53.4% for phosphorus.
[0066]
(Example 3)
Example 3 relates to an iron aluminophosphate prepared using morpholine and triethylamine as templates.
[0067]
12.5 g of 85% phosphoric acid was added to 28.05 g of water, and 6.8 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added thereto and stirred for 3 hours. A solution prepared by dissolving 8.3 g of ferrous sulfate heptahydrate in 29 g of water was added thereto, and a solution obtained by mixing 5.05 g of morpholine and 4.35 g of triethylamine was slowly added thereto, followed by further stirring for 3 hours. A gel-like starting reaction product having the following composition was obtained.
0.6FeSO₄: Al₂O₃: P₂O₅: 1.16 morpholine: 0.86 triethylamine: 70H₂O
[0068]
The mixture thus obtained was charged into a 0.2 liter stainless steel autoclave containing a Teflon (registered trademark) inner cylinder and allowed to react at 160 ° C. for 4 days in a stationary state. After the reaction, the reaction mixture was cooled and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed with water three times, filtered off and dried at 120 ° C. Table 8 shows the XRD measurement results of the obtained iron aluminophosphate.
[0069]
[Table 8]

[0070]
This sample was subjected to elemental analysis by ICP analysis in the same manner as in Example 1. As a result, the composition ratio (molar ratio) of each component with respect to the total of aluminum, phosphorus, and iron was 13.2% for iron, 38.3% for aluminum, and 48.5% for phosphorus.
[0071]
Example 4
Example 4 relates to an iron aluminophosphate prepared using morpholine and triethylamine as templates.
[0072]
11.5 g of 85% phosphoric acid was added to 26 g of water, and 5.44 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added thereto and stirred for 2 hours. A solution prepared by dissolving 8.3 g of ferrous sulfate heptahydrate in 26 g of water was added thereto, and a solution obtained by mixing 2.18 g of morpholine and 7.43 g of cyclohexylamine was slowly added thereto, followed by further stirring for 2 hours. A gel-like starting reaction product having the following composition was obtained.
0.6FeSO₄: 0.8Al₂O₃: P₂O₅: 0.5 morpholine: 1.5 cyclohexylamine: 60H₂O
[0073]
The obtained mixture was charged in a 0.2 l stainless steel autoclave containing a Teflon (registered trademark) inner cylinder, and allowed to react at 190 ° C. for 1 day in a stationary state. After the reaction, the reaction mixture was cooled and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed with water three times, filtered off and dried at 120 ° C. Table 9 shows XRD measurement results of the obtained iron aluminophosphate.
[0074]
[Table 9]

[0075]
This sample was subjected to elemental analysis by ICP analysis in the same manner as in Example 1. As a result, the constituent ratio (molar ratio) of each component with respect to the total of aluminum, phosphorus, and iron was 14.1% for iron, 38.4% for aluminum, and 47.4% for phosphorus.
[0076]
(Example 5)
Example 5 relates to a Si-containing iron aluminophosphate synthesized using morpholine and triethylamine as templates.
[0077]
11.5 g of 85% phosphoric acid was added to 28.05 g of water, and 6.8 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added thereto, followed by stirring for 3 hours. To this, 2.78 g of ferrous sulfate heptahydrate was dissolved in 29 g of water, 0.15 g of fumed silica (Aerosil 200) was added thereto, and 5.05 g of morpholine and 4.35 g of triethylamine were mixed. The solution was added slowly and stirred for an additional 3 hours. A gel-like starting reaction product having the following composition was obtained.
0.2FeSO₄: 0.05SiO₂: Al₂O₃: P₂O₅: 1.16 morpholine: 0.86 triethylamine: 70H₂O
[0078]
The obtained mixture was charged in a 0.2 l stainless steel autoclave containing a Teflon (registered trademark) inner cylinder, and allowed to react at 170 ° C. for 2 days in a stationary state. After the reaction, the reaction mixture was cooled, and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed with water three times, filtered off and dried at 120 ° C. Table 10 shows XRD measurement results of the iron aluminophosphate thus obtained.
[0079]
[Table 10]

[0080]
This sample was subjected to elemental analysis by ICP analysis in the same manner as in Example 1. As a result, the composition ratio (molar ratio) of each component with respect to the total of aluminum, phosphorus, iron, and silicon was 9.9% for iron, 2.8% for silicon, 40.7% for aluminum, and 46.7% for phosphorus. %Met.
[0081]
(Example 6)
Example 6 is an iron aluminophosphate synthesized using diisopropylethylamine and methylbutylamine as templates.
[0082]
To 15 g of water, 8.07 g of 85% phosphoric acid was added, and 3.8 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added thereto and stirred for 3 hours. A solution prepared by dissolving 3.88 g of ferrous sulfate heptahydrate in 20 g of water was added thereto, and a solution obtained by mixing 4.55 g of diisopropylethylamine and 3.05 g of methylbutylamine was slowly added thereto, followed by further stirring for 3 hours. . A gel-like starting reaction product having the following composition was obtained.
0.4FeSO₄: 0.8Al₂O₃: P₂O₅: 1 Diisopropylethylamine: 1 Methylbutylamine: 60H₂O
[0083]
The mixture thus obtained was charged into a 0.2 l stainless steel autoclave containing a Teflon (registered trademark) inner cylinder, and allowed to react at 170 ° C. for 2 days in a stationary state. After the reaction, the reaction mixture was cooled and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed with water three times, filtered off and dried at 120 ° C. Table 11 shows the XRD measurement results of the iron aluminophosphate thus obtained.
[0084]
[Table 11]

[0085]
This sample was subjected to elemental analysis by ICP analysis in the same manner as in Example 1. As a result, the constituent ratio (molar ratio) of each component with respect to the total of aluminum, phosphorus, and iron was 9.2% for iron, 42.6% for aluminum, and 48.2% for phosphorus.
[0086]
(Example 7)
Example 7 is a Si-containing CHA type iron aluminophosphate synthesized using morpholine and triethylamine as templates as templates.
[0087]
12.5 g of 85% phosphoric acid was added to 28.05 g of water, and 6.8 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added thereto and stirred for 3 hours. A solution obtained by dissolving 1.4 g of ferrous sulfate heptahydrate in 29 g of water and adding 0.3 g of fumed silica (Aerosil 200) thereto was added, and 5.05 g of morpholine and 4.35 g of triethylamine were further mixed. The solution was added slowly and stirred for an additional 3 hours. A gel-like starting reaction product having the following composition was obtained.
0.1FeSO₄: 0.1 SiO₂: Al₂O₃: P₂O₅: 1.16 morpholine: 0.86 triethylamine: 70H₂O
[0088]
The obtained mixture was charged in a 0.2 l stainless steel autoclave containing a Teflon (registered trademark) inner cylinder, and allowed to react at 160 ° C. for 3 days in a stationary state. After the reaction, the reaction mixture was cooled and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed with water three times, filtered off and dried at 120 ° C. Table 12 shows the XRD measurement results of the iron aluminophosphate thus obtained.
[0089]
[Table 12]

[0090]
This sample was subjected to elemental analysis by ICP analysis in the same manner as in Example 1. As a result, the composition ratio (molar ratio) of each component with respect to the total of aluminum, phosphorus, and iron is 6.6% for iron, 4.6% for silicon, 43.6% for aluminum, and 43.6% for phosphorus. there were.
[0091]
(Comparative example)
Synthesized according to Example 10 described in USP 4554143.
[0092]
11.6 g of 85% phosphoric acid was added to 32 g of water, and 16.4 g of alkynium isopropoxide was slowly added thereto and stirred for 3 hours. To this, 5.6 g of ferrous sulfate heptahydrate was added, and a solution obtained by mixing 42.1 g of a 35 wt% tetraethylammonium hydroxide (TEAOH) aqueous solution was further added, followed by further stirring for 3 hours. A gel-like starting reaction product having the following composition was obtained.
0.4FeSO₄: 0.8Al₂O₃: P₂O₅: 2.0 TEAOH: 68H₂O
[0093]
The obtained mixture was charged into a 0.2 l stainless steel autoclave containing a Teflon (registered trademark) inner cylinder, and allowed to react at 200 ° C. for 42 hours in a stationary state. After the reaction, the reaction mixture was cooled and the precipitate was collected by a centrifuge. The precipitate was washed with water, filtered off and dried at 120 ° C. The template-containing zeolite thus obtained was calcined for 6 hours in an air stream at 550 ° C. in the same manner as in Example 1 to obtain a calcined product.
[0094]
FIG. 3 shows an XRD diagram including a template (non-template removed product), and FIG. 4 shows an XRD diagram after firing. The XRD intensity in FIG. 3 is smaller than that in FIG. 1 of Example 1, and the crystallinity may be insufficient. In addition, in FIG. 4 after firing, a broad peak derived from amorphous around 25 ° (2θ), which is not seen in FIG. 2 after firing in Example 1, appears clearly, and near 20 ° (2θ). Shows an impurity component considered to be a dense component, and it can be seen that the structure is largely destroyed by firing.
[0095]
【The invention's effect】
As described above, according to the method for producing iron aluminophosphate of the present invention, a template selected from an alicyclic heterocyclic compound containing nitrogen, an amine having a cycloalkyl group, and an amine having an alkyl group is obtained. It is very preferable for industrial production because it is easy to use and inexpensive and has excellent safety. Furthermore, the manufactured iron aluminophosphate is easy to handle and structural destruction is less likely to occur.
[Brief description of the drawings]
FIG. 1 is an example of a typical X-ray diffraction pattern of an iron aluminophosphate produced according to the present invention.
2 is an X-ray diffraction pattern of a fired product of Example 1. FIG.
FIG. 3 is an X-ray diffraction pattern of a comparative example template-unremoved product.
FIG. 4 is an X-ray diffraction pattern of a fired product of a comparative example.

Claims (8)

A method of producing an iron aluminophosphate by hydrothermal synthesis after mixing an iron source, an aluminum source, a phosphorus source and a template,
As the template, a compound selected from one or more of two or more groups consisting of an alicyclic heterocyclic compound containing nitrogen, an amine having a cycloalkyl group and an amine having an alkyl group,
The iron aluminophosphate has at least 9.5 ± 0.3, 13.0 ± 0.3, and 16.0 ± 0.00 in powder X-ray diffraction measurement using Cu—Kα rays having an X-ray wavelength of 1.5418 mm. A method for producing iron aluminophosphate, wherein diffraction peaks appear at diffraction angles (2θ) of 3, 20.7 ± 0.3, 26.0 ± 0.3, and 30.8 ± 0.4.   A compound selected from the group consisting of two or more groups consisting of an alicyclic heterocyclic compound containing nitrogen, an amine having a cycloalkyl group, and an amine having an alkyl group, which is used as the template, is nitrogen. The method for producing an iron aluminophosphate according to claim 1, wherein the compound is an alicyclic heterocyclic compound containing at least two kinds of compounds. A method of producing an iron aluminophosphate by hydrothermal synthesis after mixing an iron source, an aluminum source, a phosphorus source and a template,
As the template, using an alicyclic heterocyclic compound containing nitrogen,
The iron aluminophosphate has at least 9.5 ± 0.3, 13.0 ± 0.3, and 16.0 ± 0.00 in powder X-ray diffraction measurement using Cu—Kα rays having an X-ray wavelength of 1.5418 mm. A method for producing iron aluminophosphate, wherein diffraction peaks appear at diffraction angles (2θ) of 3, 20.7 ± 0.3, 26.0 ± 0.3, and 30.8 ± 0.4.   The method for producing iron aluminophosphate according to any one of claims 1 to 3, wherein morpholine is used as the nitrogen-containing alicyclic heterocyclic compound. When the mixing ratio of the iron source, the aluminum source, and the phosphorus source is expressed by the molar ratio of the oxide, the value of FeO / Al ₂ O ₃ is 1.0 or less, and the value of P ₂ O ₅ / Al ₂ O ₃ is 0. The method for producing an iron aluminophosphate according to any one of claims 1 to 4, wherein the iron aluminophosphate is 6 or more.   A method for producing a calcined iron aluminophosphate, wherein the iron aluminophosphate obtained by the method for producing an iron aluminophosphate according to any one of claims 1 to 5 is further calcined. The calcined iron aluminophosphate has at least 9.5 ± 0.3, 10.1 ± 0.3, 12.8 ± 0 in powder X-ray diffraction measurement with Cu—Kα ray having an X-ray wavelength of 1.5418 mm. The diffraction peaks appear at diffraction angles (2θ) of .3, 19.5 ± 0.3, 20.4 ± 0.3, 24.3 ± 0.3, and 30.7 ± 0.4. The manufacturing method of the baked iron aluminophosphate of description. The method for producing a calcined iron aluminophosphate according to claim 6 or 7 , wherein the calcining is performed in an oxygen-containing gas atmosphere.

Images