JP2004075446A - Method for producing iron aluminophosphate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing easily treatable iron aluminophosphate in which a more inexpensive template can be used, and structure is not destroyed even by firing or the like. <P>SOLUTION: In the method for producing iron aluminophosphate by mixing an iron source, an aluminum source, a phosphorous source and a template, and thereafter hydrothermally synthesizing the same, as the template, at least one kind of compound selected from the group consisting of a nitrogen-containing cycloaliphatic heterocyclic compound, an amine having a cycloalkyl group and an amine having an alkyl group is used. At this time, one or more kinds of compounds selected from two or more groups among these groups are preferably used. Further, the nitrogen-containing cycloaliphatic heterocyclic compound is preferably used. As for the produced iron aluminophosphate, in powder X-ray diffraction measurement by Cu-Kα rays with an X-ray wavelength of 1.5418Å, diffraction peaks appear at least in the diffraction angles (2θ) of 9.5±0.3, 13.0±0.3, 16.0±0.3, 20.7±0.3, 26.0±0.3 and 30.8±0.4. <P>COPYRIGHT: (C)2004,JPO

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]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing iron aluminophosphate.
[0002]
2. Description of the Related Art
Zeolites include crystalline silicates, crystalline aluminophosphates, and the like according to the International Zeolite Association (IZA). Among those zeolites, a method for producing iron aluminophosphate, particularly using iron as a hetero atom, is described in Examples of US Pat. No. 4,554,143.
[0003]
However, in the method for producing iron aluminophosphate, an expensive tetraethylammonium salt is used as a template, and improvement in production cost has been demanded.
[0004]
In addition, when the tetraethylammonium salt is used as a template for hydrothermal synthesis, fine particles are generated and handling such as filtration is poor, and further, when the template is removed by firing, the structure is reduced. 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 in order to solve the above-described problems, and an object of the present invention is to use an iron aluminophosphate that can use a cheaper template, is easy to handle, and has a structure that 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 for solving the above-mentioned problems is a method for producing an iron aluminophosphate by hydrothermal synthesis after mixing an iron source, an aluminum source, a phosphorus source and a template, and And at least one compound selected from the group consisting of nitrogen-containing alicyclic heterocyclic compounds, amines having a cycloalkyl group, and amines having an alkyl group.
[0007]
According to the present invention, since a template is selected from nitrogen-containing alicyclic heterocyclic compounds, amines having a cycloalkyl group and amines having an alkyl group, they are easily available and inexpensive. There is an effect that the treated iron aluminophosphate is easy to handle and the structure is hardly destroyed.
[0008]
In the method for producing an iron aluminophosphate according to the present invention described above, the iron aluminophosphate is represented by a code that defines the structure of a zeolite according to the International Zeolite Association (IZA), and includes AEI, AFX, GIS, CHA, VFI, AFS, LTA, FAU, AFY and the like can be mentioned, and the followings are preferable to which CHA belongs in the code. That is, in the powder X-ray diffraction measurement using Cu-Kα ray having an X-ray wavelength of 1.5418 °, at least 9.5 ± 0.3, 13.0 ± 0.3, 16.0 ± It is characterized by being iron aluminophosphate having diffraction peaks at diffraction angles (2θ) of 0.3, 20.7 ± 0.3, 26.0 ± 0.3 and 30.8 ± 0.4.
[0009]
Further, in the method for producing an iron aluminophosphate of the present invention described above, the template may be a nitrogen-containing alicyclic heterocyclic compound, a cycloalkyl group-containing amine, or an alkyl-containing amine. It is preferable to use one or two or more selected compounds, and it is preferable to use a nitrogen-containing alicyclic heterocyclic compound as the template.
[0010]
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 represented by the molar ratio of oxide, FeO / Al ₂ O ₃ Is 1.0 or less, and P ₂ O ₅ / Al ₂ O ₃ Is 0.6 or more.
[0011]
According to the present invention, FeO / Al ₂ O ₃ Is 1.0 or less, and P ₂ O ₅ / Al ₂ O ₃ Is 0.6 or more, Fe is efficiently introduced into the skeleton structure.
[0012]
BEST MODE FOR CARRYING OUT 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 is manufactured by hydrothermal synthesis after mixing them.
[0014]
Aluminum source: The aluminum source is not particularly limited, and aluminum alkoxides such as pseudo-boehmite, aluminum isopropoxide and aluminum triethoxide, aluminum hydroxide, alumina sol, and sodium aluminate are usually used. Above all, pseudo-boehmite is preferred from the viewpoint of ease of handling and reactivity.
[0015]
Iron source: The iron source is not particularly limited, and usually, inorganic acid irons such as iron sulfate, iron nitrate, iron phosphate, iron chloride, and iron bromide, and organic acid irons such as iron acetate, iron oxalate, and iron citrate. And iron organometallic compounds such as iron pentacarbonyl and ferrocene. Among these, inorganic acid iron and organic acid iron are preferable from the viewpoint of solubility in water, and among them, divalent iron compounds such as ferrous sulfate are more preferable. In some cases, a 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: Other elements may be included in the skeleton structure as long as the powder has an X-ray diffraction pattern consisting of at least the X-ray diffraction peaks shown in Table 1. Other elements include silicon, lithium, magnesium, titanium, zirconium, vanadium, chromium, manganese, cobalt, nickel, palladium, copper, zinc, gallium, germanium, arsenic, tin, calcium, boron and the like.
[0018]
Template: The following amines are used as a template. Examples of the 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 alone. However, when a quaternary ammonium salt is used alone, poor crystallinity is liable to be formed. Therefore, at least one of the above three groups of amines may be used in 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 heteroatom is not particularly limited except nitrogen, but from the viewpoint of easiness of synthesis, a heteroatom containing oxygen in addition to nitrogen is preferable. The position of the hetero atom is not particularly limited, but it is preferable that the hetero atom is not adjacent to each other 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 hetero atom 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 preferred from the viewpoint of ease of synthesis, and morpholine is particularly preferred.
[0022]
Next, the 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 per molecule of the amine, and more preferably 1. The number of carbon atoms of the cycloalkyl group is usually 5 to 7, preferably 6. The number of cyclo rings in the cycloalkyl is not particularly limited, but usually 1 is preferred. Further, it is preferable that the cycloalkyl group is bonded to the nitrogen atom of the amine compound from the viewpoint of easy synthesis. The molecular weight is preferably 250 or less, and from the viewpoint of ease of synthesis, 200 or less is preferable, and 150 or less is more preferable.
[0023]
Examples of the amine having such a cycloalkyl group include cyclohexylamine, dicyclohexylamine, N-methylcyclohexylamine, N, N-dimethylcyclohexylamine, cyclopentylamine, and the like, and cyclohexylamine is particularly preferable.
[0024]
Next, the amine having an alkyl group will be described. In the amine having an alkyl group, the number of the alkyl group may be any number in one molecule of the amine, but is preferably 3. The number of carbon atoms of the alkyl group is preferably 4 or less, and more preferably the total number of carbon atoms of all the alkyl groups in one molecule is 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 the amine having such an alkyl group 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, and di-n-propylamine, tri-n-propylamine, tri-isopropylamine, triethylamine, di-n-butylamine, isopropylamine, t-butylamine, ethylenediamine, di-isopro Le - ethylamine, preferably in that N- methyl -n- butylamine synthetic ease, triethylamine is particularly preferred.
[0026]
These amines can be used alone or in combination of two or more as a template source and used as a raw material for hydrothermal synthesis. In the case of using one of them, (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. Among them, morpholine is particularly preferred.
[0027]
Among these, preferred combinations are a group consisting of (1) an alicyclic heterocyclic compound containing nitrogen as a hetero atom as a template, (2) an amine having a cycloalkyl group, and (3) an amine having an alkyl group. It is preferable to use one or more compounds each from two or more groups. Such a combination has an advantage / effect that it is easy to synthesize FAPO having a desired element ratio or FAPO having high crystallinity. Above all, in the case of (1) a combination of two or more kinds containing an alicyclic heterocyclic compound containing nitrogen as a hetero atom, from the viewpoint of easy synthesis of FAPO having a desired element ratio or FAPO having high crystallinity, preferable. As a specific preferred combination, a case of two or more kinds of morpholine, triethylamine and cyclohexylamine, and more preferably a combination of two or more kinds including morpholine is more preferable. The mixing ratio of each group of these templates must be selected as appropriate according to the conditions, but 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 easy synthesis of highly crystalline FAPO, 1:10 to 10: 1 is preferable, and 1: 5 to 5: 1 is more preferable. In addition, other templates may be contained, but in that case, the molar ratio is usually 20% or less, preferably 10% or less. These templates are advantageous in that they are inexpensive, easy to handle and less corrosive than conventional ones (eg, 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 the respective templates, and by reacting under preferable reaction conditions, whereby the desired structure can be obtained. Advantageous effects such as easy production of iron aluminophosphate, production of iron aluminophosphate having a stable structure that is hard to break, and suppression of generation of impurities are exhibited. 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 high crystallization rate, and the like. Therefore, in the production of the iron aluminophosphate of the present invention, a template obtained by combining a plurality of types of compounds selected from the above (1) to (3) is preferably used. There is an advantage that effects that cannot be obtained with the 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 particularly limited and may be appropriately selected depending on the conditions used. Usually, 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 product, and when the aluminum source, iron source and phosphate source are represented by the molar ratio of oxides, FeO / Al ₂ O ₃ Is generally greater than 0 and 1.0 or less, preferably 0.9 or less, and more preferably 0.8 or less.
[0032]
Also, P ₂ O ₅ / Al ₂ O ₃ 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 template affects the ease and economy of synthesis of the desired ₂ O ₅ The 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, and more preferably 2.5 or less. Further, the mixing ratio of two or more types of templates affects the ease of synthesis of a desired one and needs to be appropriately selected according to the conditions. For example, as described above, when morpholine and triethylamine are used, , The molar ratio of morpholine / triethylamine is 0.05 to 20, preferably 0.1 to 10, more preferably 0.2 to 9. The order in which at least one template selected from each of the two or more groups is selected for each group is not particularly limited, and the template may be mixed with other substances after preparation, or each template may be mixed with another substance. And may be mixed.
[0034]
Also, the proportion of water affects the ease of synthesis and economics of the desired one, ₂ O ₃ The molar ratio is usually 3 or more, preferably 5 or more, more preferably 10 or more, and usually 200 or less, preferably 150 or less, and 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, and more preferably 8 or less. It is.
[0035]
In addition, components other than the above may coexist in the aqueous gel, if desired. Advantages of coexistence include the possibility of obtaining a new effect. Examples of such components include hydroxides and salts of alkali metals and alkaline earth metals, and hydrophilic organic solvents such as alcohols. The coexistence ratio affects the easiness of synthesis of a desired product. ₂ O ₃ The molar ratio is usually 0.2 or less, preferably 0.1 or less, and 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 or less. It is as follows.
[0036]
Under these conditions, the aqueous gel is placed in a pressure-resistant container, and hydrothermal synthesis is performed by maintaining a predetermined temperature under a self-generated pressure or a gas pressure that does not inhibit crystallization, while stirring or standing.
[0037]
The reaction temperature of the 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. And more preferably 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 hydrothermal synthesis, the products are separated. The method for separating the product is not particularly limited. Usually, it is separated by filtration or decantation or the like, washed with water, and dried at a temperature from room temperature to 150 ° C. or lower to obtain a zeolite containing a template as a product. The iron aluminophosphate obtained by the production method of the present invention is excellent in crystallinity and hard to break, and thus can be easily subjected to treatment such as separation and filtration, and is industrially preferable.
[0039]
(Crystal structure)
By separation after the hydrothermal synthesis described above, an iron aluminophosphate having a powder X-ray diffraction pattern having at least the X-ray diffraction peaks in Table 1 can be obtained. FIG. 1 shows a typical powder X-ray diffraction pattern obtained at this time (see Example 1). The powdery X-ray diffraction pattern having at least the X-ray diffraction peak in Table 1 can also be obtained by calcining the iron aluminophosphate in the presence of an inert gas such as nitrogen and removing part or all of the template. Is obtained. Since the powder X-ray diffraction measurement is usually performed in the air, the sample subjected to the measurement here is one rehydrated in the atmosphere air. Further, the relative intensities in Table 1 are represented by 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 baking.
[0042]
As described above, iron aluminophosphate exhibiting at least the X-ray diffraction peak shown in Table 1 can be obtained. However, as long as it has such a characteristic in crystal structure, even if other elements are contained in the skeleton structure, good. Other elements include silicon, lithium, magnesium, titanium, zirconium, vanadium, chromium, manganese, cobalt, nickel, palladium, copper, zinc, gallium, germanium, arsenic, tin, calcium, boron, and the like. Normally, when other elements are contained in excess of the content limit, at least the X-ray diffraction peaks shown in Table 1 are not shown. Therefore, the content limit is determined as long as it shows the X-ray diffraction peak in Table 1 above. Specifically, usually, the molar ratio of other element (M) to iron (Fe) (M / Fe) Is 3 or less, preferably 2 or less, more preferably 1 or less, and still more preferably 0.5 or less.
[0043]
The iron aluminophosphate may include those having a cation species that can be exchanged for another cation, as long as it has such crystal structure characteristics. Examples of the cation in such a case include a proton, an alkali element such as Li, Na and K, an alkaline earth element such as Mg and Ca, a rare earth element such as La and Ce, and a transition metal element such as Fe, Co and Ni. Can be Among them, protons, alkali elements, and alkaline earth elements are preferable.
[0044]
The X-ray diffraction peak in Table 1 described above is data obtained from an X-ray diffraction pattern measured by a standard X-ray powder diffractometer. As a specific measuring method, using Cu as a target, using an X-ray tube with an output set to 40 kV / 30 mA as a radiation source, diffracted X-rays diffracted by the sample are monochromatized to Kα radiation by a monochromator. This is done by detecting what has happened. Optical conditions are 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). Θ is the Bragg angle observed on the recording paper. The surface spacing (d) in angstrom units is obtained from Bragg's conditional expression: 2 dsin θ = λ. Here, λ = 1.54184 °. In addition, a peak position is represented as a peak top. The intensity was measured from the height of the diffraction peak after subtracting the background, and I / I ₀ It is represented by a value of × 100. Where I ₀ Is the intensity of the strongest peak, and I is the intensity at each of the other peaks. In the case of the present invention, ₀ Is a peak at 2θ = 9.5 ± 0.3 °. In addition, usually, 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 ± 0.3 °.
[0045]
(X-ray diffraction pattern after firing)
As described above, the method for producing an iron aluminophosphate of the present invention has been described. The obtained iron aluminophosphate was further calcined in an oxygen-containing gas atmosphere, and powder X-ray diffraction measurement was performed. Table 2 shows the diffraction angle (2θ) at which the main diffraction peak of the iron aluminophosphate after calcination appears. The symbols of the relative intensities in Table 2 are the same as in Table 1.
[0046]
[Table 2]

[0047]
Iron aluminophosphate after firing shown in Table 2 can be obtained by firing iron aluminophosphate shown in Table 1 in the presence of a gas containing oxygen. The firing temperature is 200 ° C. or more and 800 ° C. or less, and is preferably 300 ° C. or more and 700 ° C. or less, and is preferably 400 ° C. or more and 650 ° C. or less from the viewpoint of easy removal of the template and / or change of the crystal structure. Is more preferred. The firing time is from 1 minute to 15 hours, and from the viewpoint of easy removal of the template and / or change of the crystal structure, preferably 2 minutes to 10 hours, more preferably 5 minutes to 8 hours. The firing time referred to here is an apparent time during which the material to be substantially fired is present in the processing temperature environment. The actual processing time may be set slightly differently. The oxygen concentration in the gas is at least 2 vol%, and is preferably at least 3 vol%, more preferably at least 5 vol%, from the viewpoint of easy removal of the template and / or change of the crystal structure. As the containing gas other than oxygen, an inert gas such as nitrogen, argon, and helium is used. In some cases, water vapor and 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 hourly space velocity (WHSV) with respect to the sample to be fired. The weight hourly space velocity (WHSV) is preferably 20 / h or less, and is preferably 15 / h or less, more preferably 10 / h or less from the viewpoint of easy removal of the template and / or change of the crystal structure. preferable. As a firing apparatus, an arbitrary heating apparatus such as a muffle furnace or a tubular furnace is used, and the firing is performed in a fixed bed or fluidized bed format.
[0048]
The calcined iron aluminophosphate thus obtained can be used as an adsorbent, a catalyst for acid and oxidation reactions, a separation material, optical materials such as quantum dots and quantum wires, semiconductor fine particles and phosphors as magnetic materials, and dyes. Widely used as a host.
[0049]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples.
[0050]
(Example 1)
Example 1 relates to an iron aluminophosphate synthesized using morpholine and triethylamine as a template.
[0051]
To a mixture of 28.05 g of water and 11.53 g of 85% phosphoric acid, 6.8 g of pseudo-boehmite (containing 25% water, manufactured by Condea) was slowly added, followed by stirring. This was designated as solution A. Separately from solution A, a solution was prepared by mixing 2.78 g of ferrous sulfate heptahydrate, 5.05 g of morpholine, 4.35 g of triethylamine, and 29 g of water. This was slowly added to the solution A and stirred for 3 hours to obtain a starting reactant having the following composition.
0.2FeSO ₄ : Al ₂ O ₃ : P ₂ O ₅ : 1.16 morpholine: 0.86 triethylamine: 70H ₂ O
[0052]
The starting reactant 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 static state. After the reaction, the mixture was cooled and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed three times with water, filtered off and dried at 120 ° C. The results of powder XRD of the iron aluminophosphate thus obtained are shown in Table 3 below. FIG. 1 shows the XRD pattern.
[0053]
[Table 3]

[0054]
The obtained iron aluminophosphate was dissolved by heating in an aqueous hydrochloric acid solution and subjected to elemental analysis by ICP analysis. The composition ratio (molar ratio) of each component to the total of aluminum, phosphorus and iron in the skeletal structure was 13%. 8.8%, aluminum 37.4%, phosphorus 48.8%.
[0055]
After that, 3 g was collected from the iron aluminophosphate containing the template, placed in a vertical quartz fired tube, heated to 550 ° C. at 1 ° C./min under an air flow of 100 ml / min, and left as it was. The firing was performed at 550 ° C. for 6 hours. The XRD of the calcined iron aluminophosphate thus obtained was measured, and the results are as shown in the following table. FIG. 2 is an XRD pattern of the fired product.
[0056]
[Table 4]

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

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

[0061]
(Example 2)
Example 2 relates to iron aluminophosphate manufactured using morpholine alone as a template.
[0062]
86.5 g of 85% phosphoric acid was added to 210 g of water, and 51 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added thereto, followed by stirring for 3 hours. A solution prepared by dissolving 41.7 g of ferrous sulfate heptahydrate in 218 g of water was added thereto, and 75.7 g of morpholine was slowly added thereto, followed by further stirring for 3 hours. Then, a gel starting reactant having the following composition was obtained.
0.4FeSO ₄ : Al ₂ O ₃ : P ₂ O ₅ : 2 morpholine: 70H ₂ O
[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 mixture was cooled, and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed three times with water, filtered off and dried at 120 ° C. Table 7 shows the 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 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 made using morpholine and triethylamine as templates.
[0067]
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, a solution of 8.3 g of ferrous sulfate heptahydrate dissolved in 29 g of water was added, and a solution obtained by mixing 5.05 g of morpholine and 4.35 g of triethylamine was slowly added, followed by stirring for 3 hours. Then, a gel starting reactant having the following composition was obtained.
0.6FeSO ₄ : Al ₂ O ₃ : P ₂ O ₅ : 1.16 morpholine: 0.86 triethylamine: 70H ₂ O
[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 mixture was cooled, and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed three times with water, filtered off and dried at 120 ° C. Table 8 shows the results of XRD measurement 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 constituent 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 iron aluminophosphate made 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, followed by stirring for 2 hours. To this was added a solution of 8.3 g of ferrous sulfate heptahydrate dissolved in 26 g of water, and a solution of a mixture of 2.18 g of morpholine and 7.43 g of cyclohexylamine was added slowly, followed by stirring for 2 hours. Then, a gel starting reactant having the following composition was obtained.
0.6FeSO ₄ ： 0.8Al ₂ O ₃ : P ₂ O ₅ : 0.5 morpholine: 1.5 cyclohexylamine: 60H ₂ O
[0073]
The obtained mixture was charged into a 0.2-liter stainless steel autoclave containing a Teflon (registered trademark) inner cylinder, and allowed to react at 190 ° C. for 1 day in a static state. After the reaction, the mixture was cooled, and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed three times with water, filtered off and dried at 120 ° C. Table 9 shows the results of XRD measurement 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 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 a template.
[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, and a solution obtained by adding 0.15 g of fumed silica (Aerosil 200) was added thereto. Further, 5.05 g of morpholine and 4.35 g of triethylamine were mixed. The solution was added slowly and stirred for another 3 hours. Then, a gel starting reactant having the following composition was obtained.
0.2FeSO ₄ : 0.05SiO ₂ : Al ₂ O ₃ : P ₂ O ₅ : 1.16 morpholine: 0.86 triethylamine: 70H ₂ O
[0078]
The obtained mixture was charged into a 0.2-liter 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 mixture was cooled, and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed three times with water, filtered off and dried at 120 ° C. Table 10 shows the results of XRD measurement 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 constituent ratio (molar ratio) of each component to the total of aluminum, phosphorus, iron, and silicon was as follows: 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]
8.07 g of 85% phosphoric acid was added to 15 g of water, and 3.8 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added thereto, followed by stirring for 3 hours. A solution obtained by dissolving 3.88 g of ferrous sulfate heptahydrate in 20 g of water was added thereto, and a mixture of 4.55 g of diisopropylethylamine and 3.05 g of methylbutylamine was slowly added thereto, followed by stirring for 3 hours. . Then, a gel starting reactant having the following composition was obtained.
0.4FeSO ₄ ： 0.8Al ₂ O ₃ : P ₂ O ₅ : 1 diisopropylethylamine: 1 methylbutylamine: 60H ₂ O
[0083]
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 170 ° C. for 2 days in a stationary state. After the reaction, the mixture was cooled, and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed three times with water, 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 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.
[0087]
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. 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) was added thereto, and 5.05 g of morpholine and 4.35 g of triethylamine were further mixed. The solution was added slowly and stirred for another 3 hours. Then, a gel starting reactant having the following composition was obtained.
0.1FeSO ₄ : 0.1SiO ₂ : Al ₂ O ₃ : P ₂ O ₅ : 1.16 morpholine: 0.86 triethylamine: 70H ₂ O
[0088]
The obtained mixture 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 3 days in a stationary state. After the reaction, the mixture was cooled, and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed three times with water, 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 to the total of aluminum, phosphorus, and iron was as follows: iron was 6.6%, silicon was 4.6%, aluminum was 43.6%, and phosphorus was 43.6%. there were.
[0091]
(Comparative example)
Synthesized according to Example 10 described in US Pat. No. 4,554,143.
[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, followed by stirring for 3 hours. To this, 5.6 g of ferrous sulfate heptahydrate was added, and a liquid obtained by further mixing 42.1 g of a 35 wt% aqueous solution of tetraethylammonium hydroxide (TEAOH) was added, and the mixture was further stirred for 3 hours. Then, a gel starting reactant having the following composition was obtained.
0.4FeSO ₄ ： 0.8Al ₂ O ₃ : P ₂ O ₅ : 2.0TEAOH: 68H ₂ O
[0093]
The obtained mixture was charged into a 0.2-liter 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 mixture was cooled and the precipitate was collected by a centrifuge. The precipitate was washed with water, separated by filtration and dried at 120 ° C. The zeolite containing the template thus obtained was fired at 550 ° C. in an air stream for 6 hours in the same manner as in Example 1 to obtain a fired product.
[0094]
FIG. 3 shows an XRD diagram of a template-containing product (without removing the template), and FIG. 4 shows an XRD diagram after firing. The XRD intensity of FIG. 3 is smaller than that of FIG. 1 of Example 1, and the crystallinity may be insufficient. In addition, in FIG. 4 after firing, a broad peak derived from amorphous near 25 ° (2θ), which is not seen in FIG. 2 after firing in Example 1, clearly appears, and near 20 ° (2θ). Indicates an impurity component considered as 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 an 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 can be obtained. It is very preferable for industrial production because it is easy to manufacture, inexpensive and excellent in safety. Furthermore, there is an unprecedented effect that the manufactured iron aluminophosphate is easy to handle and the structure is hardly destroyed.
[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.
FIG. 2 is an X-ray diffraction pattern of the fired product of Example 1.
FIG. 3 is an X-ray diffraction pattern of a sample from which a template of a comparative example has not been removed.
FIG. 4 is an X-ray diffraction pattern of a fired product of a comparative example.

Claims (5)

A method for producing iron aluminophosphate by mixing an iron source, an aluminum source, a phosphorus source and a template, followed by hydrothermal synthesis, wherein the template includes an alicyclic heterocyclic compound containing nitrogen and a cycloalkyl group. A method for producing iron aluminophosphate, comprising using at least one compound selected from the group consisting of amines and amines having an alkyl group. The iron aluminophosphate had at least 9.5 ± 0.3, 13.0 ± 0.3, 16.0 ± 0. 2. The iron aluminophos according to claim 1, wherein diffraction peaks appear at diffraction angles (2θ) of 3, 20.7 ± 0.3, 26.0 ± 0.3 and 30.8 ± 0.4. Fate manufacturing method. As the template, a compound selected from one or more selected from two or more of a group consisting of an alicyclic heterocyclic compound containing nitrogen, an amine having a cycloalkyl group, and an amine having an alkyl group may be used. The method for producing iron aluminophosphate according to claim 1 or 2, wherein: The method for producing iron aluminophosphate according to any one of claims 1 to 3, wherein an alicyclic heterocyclic compound containing nitrogen is used as the template. When the mixing ratio of the iron source, the aluminum source and the phosphorus source is represented 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 iron aluminophosphate according to any one of claims 1 to 4, wherein the iron aluminophosphate is at least 0.6.

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