JP3878940B2 - Method for producing lithium metaphosphate - Google Patents
Method for producing lithium metaphosphate Download PDFInfo
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- JP3878940B2 JP3878940B2 JP2003580213A JP2003580213A JP3878940B2 JP 3878940 B2 JP3878940 B2 JP 3878940B2 JP 2003580213 A JP2003580213 A JP 2003580213A JP 2003580213 A JP2003580213 A JP 2003580213A JP 3878940 B2 JP3878940 B2 JP 3878940B2
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- MRVHOJHOBHYHQL-UHFFFAOYSA-M lithium metaphosphate Chemical compound [Li+].[O-]P(=O)=O MRVHOJHOBHYHQL-UHFFFAOYSA-M 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000203 mixture Substances 0.000 claims description 71
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 229910052744 lithium Inorganic materials 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 16
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 13
- 229910013553 LiNO Inorganic materials 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 239000004254 Ammonium phosphate Substances 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 8
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 8
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 8
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 8
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 8
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 8
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 36
- 229910012258 LiPO Inorganic materials 0.000 description 25
- 239000000377 silicon dioxide Substances 0.000 description 18
- 229910052573 porcelain Inorganic materials 0.000 description 15
- 239000002245 particle Substances 0.000 description 14
- 229910003002 lithium salt Inorganic materials 0.000 description 7
- 159000000002 lithium salts Chemical class 0.000 description 7
- 235000011007 phosphoric acid Nutrition 0.000 description 6
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 208000016057 CHAND syndrome Diseases 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
【０００１】
【産業上の技術分野】
本発明は固相加熱反応によるメタ燐酸リチウム（ＬｉＰＯ3）の合成の新規な方法に関する。この化合物はヘキサフルオロリン酸リチウム（ＬｉＰＦ6）を合成するための中間性生物として有用である。この塩は水溶液中、非水溶液中、固相中または選択されたポリマー媒体中で良好な電解質となる。特に、本発明は従来試みられていない固体反応によりヘキサフルオロ燐酸リチウム（ＬｉＰＦ6）合成のための基礎化合物であるメタ燐酸リチウムを製造する方法に関する。
【０００２】
【従来の技術】
メタ燐酸リチウムに関する公知の文献にリチウム塩とピロ燐酸またはオルソ燐酸の加熱により得られたメタ燐酸との反応が記載されている。この反応は上記二段階の加熱処理によるもので下記反応式による[S. Sathiya Prakash, G.D.Tuli, S.K. Basu and R.D. Radan, "Advanced Inorganic Chemistry" S, Chand & Co., New Delhi, p.988(1998)]。
【０００３】
上記反応はメタ燐酸リチウムの合成のため条件を制御する必要があり、メタ燐酸リチウムの製造に複数の処理ステップを含む、水溶液から製品を得るため結晶化の処理が必要となる、等の不都合がある。
【０００５】
【発明が解決しようとする課題】
本発明の主たる目的は上述の不都合を解消してメタ燐酸リチウム（ＬｉＰＯ3）を合成する簡単で新規な方法を提供するにある。本発明の他の目的はメタ燐酸リチウム（ＬｉＰＯ3）を合成する完全な固相反応方法を提供するにある。本発明の他の目的はメタ燐酸リチウム（ＬｉＰＯ3）を得る単一ステップ処理方法を提供するにある。更に本発明の他の目的はメタ燐酸リチウム（ＬｉＰＯ3）を高収率（９０％以上）で得る方法を提供するにある。
【０００６】
【課題を解決する手段】
上記及び他の目的は本発明によるメタ燐酸リチウムを製造するための固相反応方法により達成された。従って、本発明は、リチウム原料と燐酸原料とを１：１〜２の割合で温度３００〜３５０度の範囲で固相で反応させるメタ燐酸リチウムの製造方法を提供する。
【０００７】
本発明の一実施形態においては、リチウム原料はＬｉ2Ｏ、Ｌｉ2ＣＯ3、ＬｉＯＨ、ＬｉＮＯ3またはそれらの混合物からなる群から選択される。本発明の他の実施形態においては、燐酸原料はピロ燐酸アンモニウム、燐酸アンモニウム、燐酸水素ニアンモニウム、燐酸ニ水素アンモニウムまたはそれらの混合物からなる群から選択される。本発明の他の実施形態においては、反応は固体状態において一ステップで行われる。本発明の他の実施形態においては、反応は３００〜３５０℃の温度範囲で１２時間行われ、リチウム原料はＬｉ2Ｏ、ＬｉＯＨまたはＬｉＮＯ3から選択される。
【０００８】
本発明の他の実施形態においては、反応原料は間接加熱室または電気炉で加熱される。本発明の更なる他の実施形態においては、Ｌｉ2ＣＯ3は燐酸原料と６００℃で反応させる。本発明の他の実施形態においては、リチウム原料と燐酸原料は加熱する前によく粉砕混合する。本発明の他の実施形態においては、リチウム原料と燐酸原料は等モル比で混合される。
【０００９】
【発明の実施の形態】
好ましくは等モル比のピロ燐酸アンモニウム、燐酸アンモニウム、燐酸水素ニアンモニウム、燐酸ニ水素アンモニウムをＬｉ2Ｏ、Ｌｉ2ＣＯ3、ＬｉＯＨ、ＬｉＮＯ3と間接加熱室内において３５０℃で１２時間反応させメタ燐酸リチウムを得る。メタ燐酸リチウムであることはＸ線解析により確認された。リチウム塩とピロまたはオルトアンモニウム塩との反応は下記式による。
【００１０】
１．（ＮＨ4）4Ｐ2Ｏ7＋２ＬｉＯＨ → ２ＬｉＰＯ3＋４ＮＨ3＋３Ｈ2Ｏ
２．（ＮＨ4）3ＰＯ4＋ＬｉＯＨ → ＬｉＰＯ3＋３ＮＨ3＋２Ｈ2Ｏ
３．（ＮＨ4）2ＨＰＯ4＋ＬｉＯＨ → ＬｉＰＯ3＋２ＮＨ3＋２Ｈ2Ｏ
４．（ＮＨ4）2Ｈ2ＰＯ4＋ＬｉＯＨ → ＬｉＰＯ3＋２ＮＨ3＋２Ｈ2Ｏ
【００１１】
ＬｉＰＯ3を製造する新規な方法は、Ｌｉ2Ｏ、Ｌｉ2ＣＯ3、ＬｉＯＨ、ＬｉＮＯ3とピロ燐酸アンモニウム、燐酸アンモニウム、燐酸水素ニアンモニウム、燐酸ニ水素アンモニウムとの等モル量を混合し、この混合物をよく摩砕して磁器またはシリカの坩堝に入れる。混合物中のリチウム含有量、燐含有量はモル比１：１でなければならない。混合物を入れたシリカ坩堝を電気炉に入れ、炉をゆっくり３５０℃まで加熱し、１２時間加熱して同温度に維持した。反応が終了したら炉を冷却し、製造物をよく摩砕してから純度の検査と物質の特定を行った。
【００１２】
本発明によるメタ燐酸リチウムの合成方法は、リチウム塩（Ｌｉ2Ｏ、Ｌｉ2ＣＯ3、ＬｉＯＨ、ＬｉＮＯ3）を等モル量のピロ燐酸アンモニウム、燐酸アンモニウム、燐酸水素ニアンモニウム、または燐酸ニ水素アンモニウムと混合し、混合物をよく摩砕してからシリカ坩堝にいれる。混合物の入った坩堝を電気炉中で３５０℃に連続的に加熱し、ＬｉＰＯ3を得る。反応物は固体材料で間接加熱室または電気炉で加熱される。乾燥した精製Ｌｉ2ＯまたはＬｉ2ＣＯ3またはＬｉＯＨまたはＬｉＮＯ3の必要量をピロ燐酸アンモニウム、燐酸アンモニウム、燐酸水素ニアンモニウム、燐酸ニ水素アンモニウムの何れかの燐酸塩の一つの等モル量と混合した。これらの塩中のＬｉ、Ｐの含有量は１：１の比であった。このリチウム塩とリン酸塩との混合物をよく摩砕し、摩砕した混合物をシリカ製容器に移した。容器を電気炉内に入れ、炉をゆっくり３５０℃まで加熱し連続的に１２時間加熱した。その後生成物を粉末化し純度と物質の特定のための解析を行った。
【００１３】
以下の実施例は発明を説明するためのものであり、発明の技術範囲を制限するものと解釈すべきではない。
【００１４】
実施例１
【００１５】
モル比で１：２の乾燥Ｌｉ2ＣＯ3規定量と乾燥（ＮＨ4）4Ｐ2Ｏ7規定量との混合物を調製し、この混合物を粒子サイズ５〜１０μｍとなるまで摩砕した。上記混合物をシリカ／磁器坩堝に入れ、電気炉内に配置した。混合物を最初ゆっくり加熱し６００℃で１２時間連続的に加熱した。生成物はＬｉＰＯ3であった。
【００１６】
実施例２
【００１８】
等モル比の乾燥Ｌｉ2ＣＯ3規定量と乾燥（ＮＨ4）3ＰＯ4規定量との混合物を調製し、この混合物を粒子サイズ５〜１０μｍとなるまで摩砕した。上記混合物をシリカ／磁器坩堝に入れ、電気炉内に配置した。混合物を最初ゆっくり加熱し６００℃で１２時間連続的に加熱した。生成物はＬｉＰＯ3であった。
【００１９】
実施例３
【００２１】
等モル比の乾燥Ｌｉ2ＣＯ3規定量と乾燥（ＮＨ4）2ＨＰＯ4規定量との混合物を調製し、この混合物を粒子サイズ５〜１０μｍとなるまで摩砕した。上記混合物をシリカ／磁器坩堝に入れ、電気炉内に配置した。混合物を最初ゆっくり加熱し６００℃で１２時間連続的に加熱した。生成物はＬｉＰＯ3であった。
【００２２】
実施例４
【００２４】
等モル比の乾燥Ｌｉ2ＣＯ3規定量と乾燥（ＮＨ4）ＨＰＯ4規定量との混合物を調製し、この混合物を粒子サイズ５〜１０μｍとなるまで摩砕した。上記混合物をシリカ／磁器坩堝に入れ、電気炉内に配置した。混合物を最初ゆっくり加熱し６００℃で１２時間連続的に加熱した。生成物はＬｉＰＯ3であった。
【００２５】
実施例５
【００２７】
モル比で１：２の乾燥ＬｉＯＨ規定量と乾燥（ＮＨ4）4Ｐ2Ｏ7規定量との混合物を調製し、この混合物を粒子サイズ５〜１０μｍとなるまで摩砕した。上記混合物をシリカ／磁器坩堝に入れ、電気炉内に配置した。混合物を最初ゆっくり加熱し３５０℃で１２時間連続的に加熱した。生成物はＬｉＰＯ3であった。
【００２８】
実施例６
【００３０】
等モル比の乾燥ＬｉＯＨ規定量と乾燥（ＮＨ4）2ＨＰＯ4規定量との混合物を調製し、この混合物を粒子サイズ５〜１０μｍとなるまで摩砕した。上記混合物をシリカ／磁器坩堝に入れ、電気炉内に配置した。混合物を最初ゆっくり加熱し３５０℃で１２時間連続的に加熱した。生成物はＬｉＰＯ3であった。
【００３１】
実施例７
【００３３】
等モル比の乾燥ＬｉＯＨ規定量と乾燥（ＮＨ4）2ＨＰＯ4規定量との混合物を調製し、この混合物を粒子サイズ５〜１０μｍとなるまで摩砕した。上記混合物をシリカ／磁器坩堝に入れ、電気炉内に配置した。混合物を最初ゆっくり加熱し３５０℃で１２時間連続的に加熱した。生成物はＬｉＰＯ3であった。
【００３４】
実施例８
【００３６】
モル比で１：２の乾燥ＬｉＯＨ規定量と乾燥（ＮＨ4）4Ｐ2Ｏ7規定量との混合物を調製し、この混合物を粒子サイズ５〜１０μｍとなるまで摩砕した。上記混合物をシリカ／磁器坩堝に入れ、電気炉内に配置した。混合物を最初ゆっくり加熱し３５０℃で１２時間連続的に加熱した。生成物はＬｉＰＯ3であった。
【００３７】
実施例９
【００３９】
モル比で１：２の乾燥ＬｉＮＯ3規定量と乾燥（ＮＨ4）4Ｐ2Ｏ7規定量との混合物を調製し、この混合物を粒子サイズ５〜１０μｍとなるまで摩砕した。上記混合物をシリカ／磁器坩堝に入れ、電気炉内に配置した。混合物を最初ゆっくり加熱し３５０℃で１２時間連続的に加熱した。生成物はＬｉＰＯ3であった。
【００４０】
実施例１０
【００４２】
等モル比の乾燥ＬｉＮＯ3規定量と乾燥（ＮＨ4）2ＨＰＯ4規定量との混合物を調製し、この混合物を粒子サイズ５〜１０μｍとなるまで摩砕した。上記混合物をシリカ／磁器坩堝に入れ、電気炉内に配置した。混合物を最初ゆっくり加熱し３５０℃で１２時間連続的に加熱した。生成物はＬｉＰＯ3であった。
【００４３】
実施例１１
【００４５】
等モル比の乾燥ＬｉＮＯ3規定量と乾燥（ＮＨ4）ＨＰＯ4規定量との混合物を調製し、この混合物を粒子サイズ５〜１０μｍとなるまで摩砕した。上記混合物をシリカ／磁器坩堝に入れ、電気炉内に配置した。混合物を最初ゆっくり加熱し３５０℃で１２時間連続的に加熱した。生成物はＬｉＰＯ3であった。
【００４６】
実施例１２
【００４８】
モル比で１：２の乾燥Ｌｉ2Ｏ規定量と乾燥（ＮＨ4）4Ｐ2Ｏ7規定量との混合物を調製し、この混合物を粒子サイズ５〜１０μｍとなるまで摩砕した。上記混合物をシリカ／磁器坩堝に入れ、電気炉内に配置した。混合物を最初ゆっくり加熱し３５０℃で１２時間連続的に加熱した。生成物はＬｉＰＯ3であった。
【００４９】
実施例１３
【００５１】
等モル比の乾燥Ｌｉ2Ｏ規定量と乾燥（ＮＨ4）2ＨＰＯ4規定量との混合物を調製し、この混合物を粒子サイズ５〜１０μｍとなるまで摩砕した。上記混合物をシリカ／磁器坩堝に入れ、電気炉内に配置した。混合物を最初ゆっくり加熱し３５０℃で１２時間連続的に加熱した。生成物はＬｉＰＯ3であった。
【００５２】
実施例１４
【００５４】
等モル比の乾燥Ｌｉ2Ｏ規定量と乾燥（ＮＨ4）ＨＰＯ4規定量との混合物を調製し、この混合物を粒子サイズ５〜１０μｍとなるまで摩砕した。上記混合物をシリカ／磁器坩堝に入れ、電気炉内に配置した。混合物を最初ゆっくり加熱し３５０℃で１２時間連続的に加熱した。生成物はＬｉＰＯ3であった。
【００５５】
結論
【００５７】
ピロ燐酸アンモニウム、燐酸アンモニウム、燐酸水素ニアンモニウムまたは燐酸ニ水素アンモニウムはＬｉ2Ｏ、Ｌｉ2ＣＯ3、ＬｉＯＨ、ＬｉＮＯ3のようなリチウム塩と、ＬＩとＰが等モルで、反応しＬｉＰＯ3を生成する。炭酸リチウム（Ｌｉ2ＣＯ３）の場合は６００℃で１２時間加熱する必要があるが、上記の他のリチウム塩の場合は３５０℃で１２時間加熱すればよい。生成物は白色でＸ線解析によりメタ燐酸リチウムであることが確認された。
【００５８】
【発明の効果】
１．単一ステップの加熱反応による合成方法である。
【００５９】
２．固体状態での加熱反応による方法である。
【００６０】
３．Ｌｉ2Ｏ、Ｌｉ2ＣＯ3、ＬｉＯＨ、ＬｉＮＯ3のような如何なるリチウム塩でもピロ燐酸アンモニウム、燐酸アンモニウム、燐酸水素ニアンモニウムまたは燐酸ニ水素アンモニウムと混合反応させてメタ燐酸リチウムを得ることができる。
【００６１】
４．メタ燐酸リチウムはヘキサフルオロ燐酸リチウムを合成するための基礎原料である。
【図面の簡単な説明】
【図１】 本発明による製造方法で得られた生成物のＸ線解析による結果を示す。[0001]
[Industrial technical field]
The present invention relates to a novel method for the synthesis of lithium metaphosphate (LiPO 3 ) by a solid phase heating reaction. This compound is useful as an intermediate organism to synthesize lithium hexafluorophosphate (LiPF 6 ). This salt is a good electrolyte in aqueous solution, non-aqueous solution, solid phase or selected polymer medium. In particular, the present invention relates to a method for producing lithium metaphosphate, which is a basic compound for synthesizing lithium hexafluorophosphate (LiPF 6 ) by a solid reaction that has not been attempted in the past.
[0002]
[Prior art]
The known literature on lithium metaphosphate describes the reaction of lithium salts with metaphosphoric acid obtained by heating pyrophosphoric acid or orthophosphoric acid. This reaction is based on the two-stage heat treatment described above and is based on the following reaction formula [S. Sathiya Prakash, GDTuli, SK Basu and RD Radan, "Advanced Inorganic Chemistry" S, Chand & Co., New Delhi, p.988 (1998 )].
[0003]
The above reaction requires the control of conditions for the synthesis of lithium metaphosphate, includes a plurality of processing steps in the production of lithium metaphosphate, and requires crystallization treatment to obtain a product from an aqueous solution. is there.
[0005]
[Problems to be solved by the invention]
The main object of the present invention is to provide a simple and novel method for synthesizing lithium metaphosphate (LiPO 3 ) by solving the above-mentioned disadvantages. Another object of the present invention is to provide a complete solid phase reaction method for synthesizing lithium metaphosphate (LiPO 3 ). Another object of the present invention is to provide a single-step process for obtaining lithium metaphosphate (LiPO 3 ). Another object of the present invention is to provide a method for obtaining lithium metaphosphate (LiPO 3 ) in a high yield (90% or more).
[0006]
[Means for solving the problems]
These and other objects have been achieved by a solid phase reaction method for producing lithium metaphosphate according to the present invention. Accordingly, the present invention provides a method for producing lithium metaphosphate in which a lithium raw material and a phosphoric acid raw material are reacted in a solid phase at a temperature of 300 to 350 degrees in a ratio of 1: 1 to 2.
[0007]
In one embodiment of the invention, the lithium source is selected from the group consisting of Li 2 O, Li 2 CO 3 , LiOH, LiNO 3 or mixtures thereof. In another embodiment of the invention, the phosphoric acid source is selected from the group consisting of ammonium pyrophosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, or mixtures thereof. In other embodiments of the invention, the reaction is performed in one step in the solid state. In another embodiment of the invention, the reaction is carried out in the temperature range of 300-350 ° C. for 12 hours and the lithium source is selected from Li 2 O, LiOH or LiNO 3 .
[0008]
In another embodiment of the present invention, the reaction raw material is heated in an indirect heating chamber or an electric furnace. In yet another embodiment of the present invention, Li 2 CO 3 is reacted with a phosphoric acid source at 600 ° C. In another embodiment of the present invention, the lithium source and phosphoric acid source are well pulverized and mixed before heating. In another embodiment of the present invention, the lithium source and the phosphoric acid source are mixed in an equimolar ratio.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Preferably, an equimolar ratio of ammonium pyrophosphate, ammonium phosphate, diammonium hydrogen phosphate, or ammonium dihydrogen phosphate is reacted with Li 2 O, Li 2 CO 3 , LiOH, LiNO 3 at 350 ° C. for 12 hours in an indirect heating chamber. Get lithium. It was confirmed by X-ray analysis that it was lithium metaphosphate. The reaction of lithium salt with pyro or ortho ammonium salt is according to the following formula.
[0010]
1. (NH 4 ) 4 P 2 O 7 + 2LiOH → 2LiPO 3 + 4NH 3 + 3H 2 O
2. (NH 4 ) 3 PO 4 + LiOH → LiPO 3 + 3NH 3 + 2H 2 O
3. (NH 4 ) 2 HPO 4 + LiOH → LiPO 3 + 2NH 3 + 2H 2 O
4). (NH 4 ) 2 H 2 PO 4 + LiOH → LiPO 3 + 2NH 3 + 2H 2 O
[0011]
A novel method for producing LiPO 3 is to mix Li 2 O, Li 2 CO 3 , LiOH, LiNO 3 and equimolar amounts of ammonium pyrophosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, The mixture is well ground and placed in a porcelain or silica crucible. The lithium content and phosphorus content in the mixture should be 1: 1 molar ratio. The silica crucible containing the mixture was placed in an electric furnace, and the furnace was slowly heated to 350 ° C. and heated for 12 hours to maintain the same temperature. When the reaction was completed, the furnace was cooled, the product was thoroughly ground, and the purity was checked and the substance was identified.
[0012]
The method for synthesizing lithium metaphosphate according to the present invention comprises lithium salt (Li 2 O, Li 2 CO 3 , LiOH, LiNO 3 ) in an equimolar amount of ammonium pyrophosphate, ammonium phosphate, diammonium hydrogen phosphate, or ammonium dihydrogen phosphate. The mixture is thoroughly ground and then placed in a silica crucible. The crucible containing the mixture is continuously heated to 350 ° C. in an electric furnace to obtain LiPO 3 . The reactant is heated with an indirect heating chamber or an electric furnace with a solid material. Mix the required amount of dry purified Li 2 O or Li 2 CO 3 or LiOH or LiNO 3 with one equimolar amount of either ammonium pyrophosphate, ammonium phosphate, diammonium hydrogen phosphate, or ammonium dihydrogen phosphate did. The contents of Li and P in these salts were 1: 1. The mixture of lithium salt and phosphate was well ground and the ground mixture was transferred to a silica container. The container was placed in an electric furnace and the furnace was slowly heated to 350 ° C. and continuously heated for 12 hours. The product was then pulverized and analyzed for purity and substance identification.
[0013]
The following examples are intended to illustrate the invention and should not be construed as limiting the scope of the invention.
[0014]
Example 1
[0015]
A mixture of a dry Li 2 CO 3 normal amount and a dry (NH 4 ) 4 P 2 O 7 normal amount in a molar ratio of 1: 2 was prepared, and the mixture was ground to a particle size of 5-10 μm. The above mixture was placed in a silica / porcelain crucible and placed in an electric furnace. The mixture was first slowly heated and continuously heated at 600 ° C. for 12 hours. The product was LiPO 3 .
[0016]
Example 2
[0018]
A mixture of an equimolar ratio of dry Li 2 CO 3 normal and dry (NH 4 ) 3 PO 4 normal was prepared and this mixture was ground to a particle size of 5-10 μm. The above mixture was placed in a silica / porcelain crucible and placed in an electric furnace. The mixture was first slowly heated and continuously heated at 600 ° C. for 12 hours. The product was LiPO 3 .
[0019]
Example 3
[0021]
A mixture of an equimolar ratio of dry Li 2 CO 3 normal and dry (NH 4 ) 2 HPO 4 normal was prepared and the mixture was ground to a particle size of 5-10 μm. The above mixture was placed in a silica / porcelain crucible and placed in an electric furnace. The mixture was first slowly heated and continuously heated at 600 ° C. for 12 hours. The product was LiPO 3 .
[0022]
Example 4
[0024]
A mixture of an equimolar ratio of dry Li 2 CO 3 normal and dry (NH 4 ) HPO 4 normal was prepared and the mixture was ground to a particle size of 5-10 μm. The above mixture was placed in a silica / porcelain crucible and placed in an electric furnace. The mixture was first slowly heated and continuously heated at 600 ° C. for 12 hours. The product was LiPO 3 .
[0025]
Example 5
[0027]
A mixture of 1: 2 dry LiOH and a dry (NH 4 ) 4 P 2 O 7 normal in a molar ratio was prepared and the mixture was ground to a particle size of 5-10 μm. The above mixture was placed in a silica / porcelain crucible and placed in an electric furnace. The mixture was first slowly heated and continuously heated at 350 ° C. for 12 hours. The product was LiPO 3 .
[0028]
Example 6
[0030]
A mixture of equimolar ratios of dry LiOH and dry (NH 4 ) 2 HPO 4 was prepared and the mixture was ground to a particle size of 5-10 μm. The above mixture was placed in a silica / porcelain crucible and placed in an electric furnace. The mixture was first slowly heated and continuously heated at 350 ° C. for 12 hours. The product was LiPO 3 .
[0031]
Example 7
[0033]
A mixture of equimolar ratios of dry LiOH and dry (NH 4 ) 2 HPO 4 was prepared and the mixture was ground to a particle size of 5-10 μm. The above mixture was placed in a silica / porcelain crucible and placed in an electric furnace. The mixture was first slowly heated and continuously heated at 350 ° C. for 12 hours. The product was LiPO 3 .
[0034]
Example 8
[0036]
A mixture of 1: 2 dry LiOH and a dry (NH 4 ) 4 P 2 O 7 normal in a molar ratio was prepared and the mixture was ground to a particle size of 5-10 μm. The above mixture was placed in a silica / porcelain crucible and placed in an electric furnace. The mixture was first slowly heated and continuously heated at 350 ° C. for 12 hours. The product was LiPO 3 .
[0037]
Example 9
[0039]
A mixture of dry LiNO 3 normal and dry (NH 4 ) 4 P 2 O 7 normal in a molar ratio of 1: 2 was prepared and the mixture was ground to a particle size of 5-10 μm. The above mixture was placed in a silica / porcelain crucible and placed in an electric furnace. The mixture was first slowly heated and continuously heated at 350 ° C. for 12 hours. The product was LiPO 3 .
[0040]
Example 10
[0042]
A mixture of an equimolar ratio of dry LiNO 3 normal and dry (NH 4 ) 2 HPO 4 normal was prepared and the mixture was ground to a particle size of 5-10 μm. The above mixture was placed in a silica / porcelain crucible and placed in an electric furnace. The mixture was first slowly heated and continuously heated at 350 ° C. for 12 hours. The product was LiPO 3 .
[0043]
Example 11
[0045]
A mixture of equimolar ratios of dry LiNO 3 normal and dry (NH 4 ) HPO 4 normal was prepared and the mixture was ground to a particle size of 5-10 μm. The above mixture was placed in a silica / porcelain crucible and placed in an electric furnace. The mixture was first slowly heated and continuously heated at 350 ° C. for 12 hours. The product was LiPO 3 .
[0046]
Example 12
[0048]
A mixture of a dry Li 2 O defined amount and a dry (NH 4 ) 4 P 2 O 7 defined amount of 1: 2 in molar ratio was prepared, and the mixture was ground to a particle size of 5-10 μm. The above mixture was placed in a silica / porcelain crucible and placed in an electric furnace. The mixture was first slowly heated and continuously heated at 350 ° C. for 12 hours. The product was LiPO 3 .
[0049]
Example 13
[0051]
A mixture of an equimolar ratio of dry Li 2 O defined amount and dry (NH 4 ) 2 HPO 4 defined amount was prepared and the mixture was ground to a particle size of 5-10 μm. The above mixture was placed in a silica / porcelain crucible and placed in an electric furnace. The mixture was first slowly heated and continuously heated at 350 ° C. for 12 hours. The product was LiPO 3 .
[0052]
Example 14
[0054]
The mixture of dry Li 2 O defined amount equimolar ratio and drying (NH 4) HPO 4 specified amount were prepared and milled the mixture until the particle size 5 to 10 [mu] m. The above mixture was placed in a silica / porcelain crucible and placed in an electric furnace. The mixture was first slowly heated and continuously heated at 350 ° C. for 12 hours. The product was LiPO 3 .
[0055]
Conclusion [0057]
Ammonium pyrophosphate, ammonium phosphate, diammonium hydrogen phosphate, or ammonium dihydrogen phosphate react with lithium salt such as Li 2 O, Li 2 CO 3 , LiOH, LiNO 3 and LI and P in equimolar amounts to react with LiPO 3 . Generate. In the case of lithium carbonate (Li 2 CO 3), it is necessary to heat at 600 ° C. for 12 hours, but in the case of the other lithium salts described above, it may be heated at 350 ° C. for 12 hours. The product was white and was confirmed to be lithium metaphosphate by X-ray analysis.
[0058]
【The invention's effect】
1. It is a synthesis method by a single-step heating reaction.
[0059]
2. This is a method by a heating reaction in a solid state.
[0060]
3. Any lithium salt such as Li 2 O, Li 2 CO 3 , LiOH, or LiNO 3 can be mixed and reacted with ammonium pyrophosphate, ammonium phosphate, diammonium hydrogen phosphate, or ammonium dihydrogen phosphate to obtain lithium metaphosphate.
[0061]
4). Lithium metaphosphate is a basic raw material for synthesizing lithium hexafluorophosphate.
[Brief description of the drawings]
FIG. 1 shows the result of X-ray analysis of a product obtained by the production method according to the present invention.
Claims (9)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/IN2002/000081 WO2003082736A1 (en) | 2002-03-28 | 2002-03-28 | Process for the preparation of lithium metaphosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005519842A JP2005519842A (en) | 2005-07-07 |
| JP3878940B2 true JP3878940B2 (en) | 2007-02-07 |
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| JP2003580213A Expired - Fee Related JP3878940B2 (en) | 2002-03-28 | 2002-03-28 | Method for producing lithium metaphosphate |
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| JP (1) | JP3878940B2 (en) |
| AU (1) | AU2002249551A1 (en) |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101616893B1 (en) | 2014-06-30 | 2016-05-02 | 재단법인 포항산업과학연구원 | Mehod of preparing meta lithium phosphate |
-
2002
- 2002-03-28 JP JP2003580213A patent/JP3878940B2/en not_active Expired - Fee Related
- 2002-03-28 AU AU2002249551A patent/AU2002249551A1/en not_active Abandoned
- 2002-03-28 DE DE10296691T patent/DE10296691T5/en not_active Ceased
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101616893B1 (en) | 2014-06-30 | 2016-05-02 | 재단법인 포항산업과학연구원 | Mehod of preparing meta lithium phosphate |
Also Published As
| Publication number | Publication date |
|---|---|
| DE10296691T5 (en) | 2004-04-22 |
| AU2002249551A1 (en) | 2003-10-13 |
| JP2005519842A (en) | 2005-07-07 |
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