JPH049734B2 - - Google Patents
Info
- Publication number
- JPH049734B2 JPH049734B2 JP17845384A JP17845384A JPH049734B2 JP H049734 B2 JPH049734 B2 JP H049734B2 JP 17845384 A JP17845384 A JP 17845384A JP 17845384 A JP17845384 A JP 17845384A JP H049734 B2 JPH049734 B2 JP H049734B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- ions
- metal
- formula
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- -1 metal complex ions Chemical class 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 150000003863 ammonium salts Chemical class 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 229910052787 antimony Inorganic materials 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 229910052733 gallium Inorganic materials 0.000 claims description 8
- 229910052735 hafnium Inorganic materials 0.000 claims description 8
- 229910052741 iridium Inorganic materials 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 229910052732 germanium Inorganic materials 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims description 2
- 125000003544 oxime group Chemical group 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims 1
- 229910052745 lead Inorganic materials 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 239000002994 raw material Substances 0.000 description 7
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 150000002923 oximes Chemical class 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical group 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- RJYDMIMSSMCNIG-UHFFFAOYSA-N (2-octylphenyl) dihydrogen phosphate Chemical compound CCCCCCCCC1=CC=CC=C1OP(O)(O)=O RJYDMIMSSMCNIG-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
〔産業上の利用分野〕
本発明は、Ag、Ｂ、Bi、Cr、Ir、Ga、Ge、
Mn、Li、Pb、Sb、Sn、Ti、Hf及びZrの各金属
のフツ素含有アンモニウム塩を製造する方法に関
する。
〔従来の技術〕
従来、これらの金属（Ag、Ｂ、Bi、Cr、Ir、
Ga、Ge、Mn、Li、Pb、Sb、Sn、Ti、Hf及び
Zr）のフツ素含有アンモニウム塩の製造する方
法としては、上記金属を含有する原料例えば酸化
物をフツ酸で溶解するか、または金属をフツ酸で
溶解した後、アンモニアガス又はアンモニア水で
中和し、次に水溶液を蒸発濃縮することにより造
られる。
〔発明が解決しようとする問題点〕
しかし、このような方法で純粋なフツ化アンモ
ニウム化合物を造ろうとすれば、まず原料酸化物
または金属自体を高純度にしたものを使用する必
要があり、天然に存在する原料から製造するには
極めて長く複雑な工程を必要とし、且つ高価とな
る欠点があつた。
本発明は上記金属のフツ素含有アンモニウム塩
を製造するにあたり上述の従来法に於ける欠点の
ない比較的安価な方法で高純度な上記金属のフツ
素含有アンモニウム塩の提供を目的とするもので
ある。
本発明は、高価な精製原料を使用することな
く、一般に天然に存在する鉱物資源から、あるい
は産業廃棄物のような資源から、抽出により上記
金属のフツ化アンモニウムを製造する方法に関す
るもので、従来法における原料の種々の精製工程
を要することや、原料価格が高い等の問題を克服
するものである。
〔問題点を解決するための手段〕
本発明は、アルキル燐酸の群、アルキル・アリ
ール燐酸の群、アルキルサルフアイドの群、カル
ボン酸の群、オキシムの群、ケトンの群、中性燐
酸エステルの群、炭素数４〜25の高級アルコール
の群、及び第１級〜第４級アミンの各群から成る
群から選択された１種又は２種以上の抽出剤を石
油系炭化水素で希釈してなる有機溶媒に抽出含有
されているAg、Ｂ、Bi、Cr、Ir、Ga、Ge、
Mn、Li、Pb、Sb、Sn、Ti、Hf及びZrのイオン
又はこれらの金属錯イオンの１種を含む有機溶媒
と、F-イオン及びNH+ 4イオンを含有する水溶液
とを接触させることにより、上記金属イオン又は
金属錯イオンを水相に移行させて、Ag、Ｂ、Bi、
Cr、Ir、Ga、Ge、Mn、Li、Pb、Sb、Sn、Ti、
Hf及びZrのフツ素含有金属アンモニウム塩を造
ると共に該有機溶媒を再生させることを特徴とす
るフツ素含有金属アンモニウム塩の製造方法であ
る。
本発明はまず、Ag、Ｂ、Bi、Cr、Ir、Ga、
Ge、Mn、Li、Pb、Sb、Sn、Ti、Hf及びZr金属
を含有する鉱物資源あるいは産業廃棄物等の任意
の資源から上記金属を含有する水溶液を造り、こ
れをアルキル燐酸の群、アルキル・アリール燐酸
の群、アルキルサルフアイドの群、カルボン酸の
群、オキシムの群、ケトンの群、中性燐酸エステ
ルの群、炭素数４〜25の高級アルコールの群、及
び第１級〜第４級アミンの各群から成る群から選
択された１種又は２種以上の抽出剤を石油系炭化
水素で希釈してなる有機溶媒によつて、下記にそ
の一例を示すように、それ自体既知の操作で抽出
して出発原料を得る：
A+ g＋Ｒ・Ｈ→Ｒ・Ag＋H+
（水相） （有機相）（有機相）（水相）
Ｂ（OH）- 4＋（HO−Ｒ−OH）2→Ｂ（RO2）2＋2H2O
Bi3+＋3R・Ｈ→R3Bi＋3H+
Cr3+＋R3H+→R3Cr＋3H+
IrCl2- 6＋2R3NH+→（R3NH）2IrCl6
Ge2+＋2R・H+→R2・Ge＋2H+
Ca3+＋3RH→R3Ga＋3H+
Mn2+＋2RH→R2Mn＋2H+
Li＋（HO−Ｒ−OH）→Li（Ｏ−Ｒ−OH）＋H+
Pb2＋2RH→R2Pb＋2H+
Sb3+＋3RH→R3Sb＋3H+
Sn2+＋2RH→R2Sn＋2H+
Ti3+＋3RH→R3Ti＋3H+
HfCl4＋MIBK→MIBK・HfCl4
Zr（NO3）4＋2TBP→（TBP）2Zr（NO3）4
上式中R.H+はアルキル燐酸の群、カルボン酸
の群、及びヒドロキシオキシムの群のように、Ｈ
型変換基を持つ抽出剤を示す。
また、ROHは高級アルコールを示し、MIBK
（メチルイソブチルケトン）、TBP（トリブチルホ
スフエート）、R3NH+は第３級アミンを示す。
抽出種は各金属ともその一例を示したにすぎ
ず、本発明はこれに限定されるものではない。
有機溶媒中に抽出されたこれらの金属イオン又
は金属錯イオンは該有機溶媒をF-イオン及び
NH+ 4イオンを含有する水溶液と接触させること
により、下式に示すように有機溶媒中より金属イ
オン又は金属錯イオンを水相に移行させフルオロ
金属アンモニウムの結晶を得ると共に、有機溶媒
を再生させる；
Ｒ・Ag＋NH4HF2→Ｒ・Ｈ＋NH4AgF2
Ｂ（RO2）2＋2NH4HF2＋2HF→２（HO
−Ｒ−OH）＋NH4BF4＋NH4F
R3Bi＋3NH4HF2→3RH＋（NH4）3BiF6
R3Cr＋3NH4HF2→3RH＋（NH4）3CrF6
（R3NH+）2IrCl6＋6NH4F→２（R3NH）Cl＋（NH4）2IrF6
＋4NH4Cl
R2Ge＋2NH4HF2→2RH＋（NH4）2GeF4
R3Ge＋3NH4HF2→3RH＋（NH4）3GeF6
R2Mn＋2NH4HF2→2RH＋（NH4）2MnF4
Li（Ｏ−Ｒ−OH）＋NH4HF2＋2HF
→HO−Ｒ−OH＋NH4LiF4＋2H+
R2Pb＋2NH4HF2→2RH＋（NH4）2PbF4
R3Sb＋3NH4HF2→3RH＋（NH4）3SbF6
R2Sn＋2NH4HF2→2RH＋（（NH4）2SnF4
R3Ti＋3NH4HF2→3RH＋（NH4）3TiF6
MIBKHfCl4＋6NH4F→MIBK
＋（NH4）2HfF6＋4NH4Cl
（TBP）2（ZrNO3）4＋6NH4F→2TBP
＋（NH4）2ZrF6＋4NH4NO3
水相に移行した各種金属イオン及び各種金属錯
イオンはフツ素含有化合物となり、これらは水溶
液に対して、フツ化物に比較して溶解度も小さ
く、しかも結晶成長速度が極めて大きいという特
長があり、容易にフツ素含有アンモニウムの塩、
すなわちフルオロ金属アンモニウムの結晶が得ら
れる。
上式で示されたフツ素含有アンモニウム塩は、
上記に示す以外の化合物も存在し、工業的には純
粋な結晶でなく、混合物であることが多く、ある
いは原子価の異なる塩が混入する場合もあり得
る。これは、フツ素含有アンモニウム塩が生成す
る水溶液の条件により異なるので一定でないこと
が多く、従つて本発明は、上記に示す反応式に限
定されるものではない。
本発明で使用するアルキル燐酸は、次の群より
選択される：
[Industrial Application Field] The present invention is applicable to Ag, B, Bi, Cr, Ir, Ga, Ge,
The present invention relates to a method for producing fluorine-containing ammonium salts of Mn, Li, Pb, Sb, Sn, Ti, Hf, and Zr metals. [Prior art] Conventionally, these metals (Ag, B, Bi, Cr, Ir,
Ga, Ge, Mn, Li, Pb, Sb, Sn, Ti, Hf and
The method for producing the fluorine-containing ammonium salt of Zr) includes dissolving the above-mentioned metal-containing raw material, such as an oxide, in hydrofluoric acid, or dissolving the metal in hydrofluoric acid, and then neutralizing it with ammonia gas or aqueous ammonia. and then evaporating the aqueous solution. [Problems to be solved by the invention] However, in order to produce pure ammonium fluoride compounds using this method, it is first necessary to use highly purified raw material oxides or the metal itself, and natural Production from raw materials that exist in the world requires extremely long and complicated steps, and has the disadvantage of being expensive. The object of the present invention is to provide a highly pure fluorine-containing ammonium salt of the above-mentioned metal by a relatively inexpensive method that does not have the drawbacks of the conventional methods described above. be. The present invention relates to a method for producing ammonium fluoride of the above metal by extraction from naturally occurring mineral resources or resources such as industrial waste without using expensive refined raw materials. This method overcomes problems such as the necessity of various refining processes for raw materials and the high cost of raw materials in the conventional method. [Means for Solving the Problems] The present invention provides a group of alkyl phosphoric acids, a group of alkyl/aryl phosphoric acids, a group of alkyl sulfides, a group of carboxylic acids, a group of oximes, a group of ketones, a group of neutral phosphoric esters, one or more extractants selected from the group consisting of C4-25, higher alcohols having 4 to 25 carbon atoms, and primary to quaternary amines are diluted with petroleum-based hydrocarbons. Ag, B, Bi, Cr, Ir, Ga, Ge,
By contacting an organic solvent containing Mn, Li, Pb, Sb, Sn, Ti, Hf, and Zr ions or one of these metal complex ions with an aqueous solution containing F - ions and NH + 4 ions. , the above metal ions or metal complex ions are transferred to the aqueous phase to produce Ag, B, Bi,
Cr, Ir, Ga, Ge, Mn, Li, Pb, Sb, Sn, Ti,
A method for producing a fluorine-containing metal ammonium salt of Hf and Zr, which is characterized by producing the fluorine-containing metal ammonium salt and regenerating the organic solvent. The present invention first focuses on Ag, B, Bi, Cr, Ir, Ga,
An aqueous solution containing the above metals is prepared from any resource such as mineral resources or industrial waste containing Ge, Mn, Li, Pb, Sb, Sn, Ti, Hf, and Zr metals, - Aryl phosphoric acid group, alkyl sulfide group, carboxylic acid group, oxime group, ketone group, neutral phosphoric ester group, higher alcohol group having 4 to 25 carbon atoms, and primary to quaternary With an organic solvent obtained by diluting one or more extractants selected from the group consisting of class amines with petroleum hydrocarbons, as shown in the example below, The starting material is obtained by extraction by operation: A + g + R・H→R・Ag+H + (aqueous phase) (organic phase) (organic phase) (aqueous phase) B (OH) - 4 + (HO−R−OH ) 2 →B(RO 2 ) 2 +2H 2 O Bi 3+ +3R・H→R 3 Bi+3H + Cr 3+ +R 3 H + →R 3 Cr+3H + IrCl 2- 6 +2R 3 NH + →(R 3 NH) 2 IrCl 6 Ge 2+ +2R・H + →R 2・Ge+2H + Ca 3+ +3RH→R 3 Ga+3H + Mn 2+ +2RH→R 2 Mn+2H + Li+(HO−R−OH)→Li(O−R−OH) +H + Pb 2 +2RH→R 2 Pb+2H + Sb 3+ +3RH→R 3 Sb+3H + Sn 2+ +2RH→R 2 Sn+2H + Ti 3+ +3RH→R 3 Ti+3H + HfCl 4 +MIBK→MIBK・HfCl 4 Zr (NO 3 ) 4 +2TBP→(TBP) 2 Zr(NO 3 ) 4 In the above formula, RH + is H
Indicates an extractant with a type conversion group. Also, ROH indicates higher alcohol and MIBK
(methyl isobutyl ketone), TBP (tributyl phosphate), and R 3 NH + represent a tertiary amine. The extracted species are merely examples of each metal, and the present invention is not limited thereto. These metal ions or metal complex ions extracted into the organic solvent transform the organic solvent into F - ions and
By contacting with an aqueous solution containing NH + 4 ions, metal ions or metal complex ions are transferred from the organic solvent to the aqueous phase to obtain crystals of fluorometallic ammonium as shown in the formula below, and the organic solvent is regenerated. ; R・Ag+NH 4 HF 2 →R・H+NH 4 AgF 2 B(RO 2 ) 2 +2NH 4 HF 2 +2HF→2(HO −R−OH)+NH 4 BF 4 +NH 4 F R 3 Bi+3NH 4 HF 2 →3RH+(NH 4 ) 3 BiF 6 R 3 Cr+3NH 4 HF 2 →3RH+(NH 4 ) 3 CrF 6 (R 3 NH + ) 2 IrCl 6 +6NH 4 F→2(R 3 NH)Cl+(NH 4 ) 2 IrF 6
+4NH 4 Cl R 2 Ge+2NH 4 HF 2 →2RH+(NH 4 ) 2 GeF 4 R 3 Ge+3NH 4 HF 2 →3RH+(NH 4 ) 3 GeF 6 R 2 Mn+2NH 4 HF 2 →2RH+(NH 4 ) 2 MnF 4 Li( O-R-OH) +NH 4 HF 2 +2HF →HO-R-OH+NH 4 LiF 4 +2H + R 2 Pb+2NH 4 HF 2 →2RH+ (NH 4 ) 2 PbF 4 R 3 Sb+3NH 4 HF 2 →3RH+ (NH 4 ) 3 SbF 6 R 2 Sn+2NH 4 HF 2 →2RH+((NH 4 ) 2 SnF 4 R 3 Ti+3NH 4 HF 2 →3RH+(NH 4 ) 3 TiF 6 MIBKHfCl 4 +6NH 4 F→MIBK +(NH 4 ) 2 HfF 6 +4NH 4 Cl (TBP) 2 (ZrNO 3 ) 4 +6NH 4 F→2TBP + (NH 4 ) 2 ZrF 6 +4NH 4 NO 3Various metal ions and various metal complex ions transferred to the aqueous phase become fluorine-containing compounds, which are dissolved in an aqueous solution. However, compared to fluoride, it has a low solubility and an extremely high crystal growth rate, so it is easy to form fluorine-containing ammonium salts,
That is, crystals of fluorometallic ammonium are obtained. The fluorine-containing ammonium salt shown in the above formula is
Compounds other than those shown above also exist, and industrially they are often not pure crystals but mixtures, or salts with different valences may be mixed. This is often not constant because it varies depending on the conditions of the aqueous solution in which the fluorine-containing ammonium salt is produced; therefore, the present invention is not limited to the reaction formula shown above. The alkyl phosphoric acid used in the invention is selected from the following group:
【式】【formula】
【式】【formula】
【式】または[expression] or
【式】
（式中、Ｒはアルキル基を示し、一般に炭素数
が４〜22のものが使用される）
以下に示む実施例中に記載するD2EHPA（ジー
２−エチルヘキシル燐酸）は上記式(イ)の群に属
し、アルキル基はC8H17のものである。
次に本発明で用いられるケトンは、次の群より
選択される：
（式中、Ｒ，R′はアルキル基またはアリール
基を示し、それぞれ炭素数３〜15のものがよく使
用される）
また、シクロヘキサノン（C6H12O）もよく用
いられる。
本発明で使預するアルキル・アリール燐酸の群
は次に示す化合物より選択される：
（式中、Ｒは４〜15個の炭素原子を含むアルキ
ル基で、Ａはアリール基（フエニール基、トリル
基又はキシリル基）を示す）
実施例中に示すOPPA（オクチルフエニール燐
酸）はＲ＝C8H17、Ａ＝C6H5の化合物をいう。
本発明で抽出剤として使用するカルボン酸は次
の群より撰選される：[Formula] (In the formula, R represents an alkyl group, and those having 4 to 22 carbon atoms are generally used.) D 2 EHPA (di-2-ethylhexyl phosphoric acid) described in the examples shown below is It belongs to the group of formula (a), and the alkyl group is C 8 H 17 . The ketones used in the present invention are then selected from the following group: (In the formula, R and R' represent an alkyl group or an aryl group, and those having 3 to 15 carbon atoms are often used.) Cyclohexanone (C 6 H 12 O) is also often used. The group of alkyl aryl phosphoric acids employed in the present invention is selected from the following compounds: (In the formula, R is an alkyl group containing 4 to 15 carbon atoms, and A represents an aryl group (phenyl group, tolyl group, or xylyl group)) OPPA (octyl phenyl phosphoric acid) shown in the examples is R = C 8 H 17 and A = C 6 H 5 . The carboxylic acids used as extractants in the present invention are selected from the following groups:
【式】 [Formula]
【式】
（式中、Ｒはアルキル基を示し、一般に炭素数
が４〜22のものが使用される）
実施例に記載しているＶ−10（パーサテイツク
−10、シエル化学(株)商品名）は上記(イ)の群に属
し、アルキル基の炭素数が９〜11の範囲のもので
ある。
本発明で使用するオキシムは次の群より選択さ
れる：
（式中、ＲはＨ、C6H5、CH3、[Formula] (In the formula, R represents an alkyl group, and those having 4 to 22 carbon atoms are generally used.) ) belongs to the group (a) above, and the number of carbon atoms in the alkyl group is in the range of 9 to 11. The oximes used in the present invention are selected from the following group: (In the formula, R is H, C 6 H 5 , CH 3 ,
【式】 又は【formula】 or
【式】であり、ＸはCl又はＨで
ある）また、これらと類似のオキシムも当然使用
できる。
実施例に示すLi×64N（ヘンケル化学(株)商品名）
の如き２種以上のヒドロキシオキシムを混合し、
上記オキシムと同等の特性をもつものも充分使用
できる。
本発明で使用する中性燐酸エステルは次の群よ
り選択される：[Formula] and X is Cl or H) Also, oximes similar to these can of course be used. Li×64N (trade name of Henkel Chemical Co., Ltd.) shown in the example
Mixing two or more hydroxyoximes such as
Oximes having the same properties as the above oximes can also be used. The neutral phosphoric esters used in the present invention are selected from the following group:
【式】 [Formula]
【式】又は[Formula] or
【式】
（上式中、Ｒは炭素数４〜22のアルキル基のも
のが使用される）
実施例に示すTBP（トリブチルホスフエート）
は上記(イ)の群に属し、ＲはC4H9のものをいう。
次に本発明で使用するアルキルサルフアイドは
次の群より選択される：
Ｒ−Ｓ−Ｒ
（式中Ｒはアルキル基を示し、一般に炭素数４
〜14のものが使用される）
以下に示す実施例中に記載するRSRはジ−ｎ
−ヘキシルサルフアイドを示し、アルキル基が
C6H13のものである。
本発明で使用する高級アルコールはROH、
R2OH、又はR3OH（Ｒはアルキル基を示す）で
示され、炭素数４〜25のものが使用される。
次に本発明で使用する第１級〜第４級アミンは
次の群より選択される：
第１級アミン RNH2
（式中Ｒは炭素数４〜25のアルキル基である）
第２級アミン R2N−又はR2NH
（式中Ｒは炭素数が４〜25のアルキル基であ
る）
第３級アミン R3N−又はR3NH−
（式中Ｒは炭素数が４〜22のアルキル基であ
る）
実施例で使用するTOA（トリオクチルアミン）
を次に示す：
但しClを他のアニオンで置換することができ
る。
第４級アミン[Formula] (In the above formula, R is an alkyl group having 4 to 22 carbon atoms.) TBP (tributyl phosphate) shown in Examples
belongs to the group (a) above, and R refers to C 4 H 9 . The alkyl sulfide used in the present invention is then selected from the following group: R-S-R, where R represents an alkyl group, generally having 4 carbon atoms.
~14 are used) The RSR described in the examples shown below is G-n
-Hexyl sulfide, where the alkyl group is
It is of C 6 H 13 . The higher alcohol used in the present invention is ROH,
It is represented by R 2 OH or R 3 OH (R represents an alkyl group) and has 4 to 25 carbon atoms. The primary to quaternary amines used in the present invention are then selected from the following group: Primary amines RNH 2 (wherein R is an alkyl group having 4 to 25 carbon atoms) Secondary amines R 2 N- or R 2 NH (in the formula, R is an alkyl group having 4 to 25 carbon atoms) Tertiary amine R 3 N- or R 3 NH- (in the formula, R is an alkyl group having 4 to 22 carbon atoms) TOA (trioctylamine) used in the examples
is shown below: However, Cl can be replaced with other anions. Quaternary amine
以下実施例を掲げて本発明を説明する。
実施例
表に示す各金属イオン又は金属錯イオン含有水
溶液にそれぞれ公知の抽出条件にて、金属イオン
又は金属錯イオンを抽出せしめ、これらの金属イ
オン又は金属錯イオンを含有する出発原料より下
表に示す有機溶媒を使用し、及び剥離液を使用し
てフルオロ金属アンモニウム塩を造つた。
The present invention will be explained below with reference to Examples. Example Metal ions or metal complex ions were extracted from each metal ion or metal complex ion-containing aqueous solution shown in the table under known extraction conditions, and the starting materials containing these metal ions or metal complex ions were extracted as shown in the table below. Fluorometal ammonium salts were made using the organic solvents shown and the stripping solution.
本発明によれば、高価な原料を使用することな
く、しかも単純な工程で所定金属のフルオロ金属
（Ag、Ｂ、Bi、Cr、Ir、Ga、Ge、Mn、Li、Pb、
Sb、Sn、Ti、Hf及びZr）アンモニウムの塩をつ
くることができる。
According to the present invention, fluoro-metals (Ag, B, Bi, Cr, Ir, Ga, Ge, Mn, Li, Pb,
Sb, Sn, Ti, Hf and Zr) ammonium salts can be made.
第１図は本発明方法の工程図、第２図は本発明
で原料として使用する金属イオン又は金属錯イオ
ンを抽出し含有する有機溶媒を造る工程図であ
る。
図中、Ａ……金属イオン又は金属錯イオンを含
有する有機溶媒、Ｂ……NH+ 4イオンとF-イオン
を含有する溶液、Ｃ……剥離工程、Ｄ……晶析工
程、Ｅ……フルオロ金属アンモニウムの結晶、Ｆ
……金属イオン又は金属錯イオンを含有する水溶
液、Ｇ……抽出工程。なお、各図中同一符号は同
一又は相当部分を示す。
FIG. 1 is a process diagram of the method of the present invention, and FIG. 2 is a process diagram of producing an organic solvent containing extracted metal ions or metal complex ions used as raw materials in the present invention. In the figure, A...organic solvent containing metal ions or metal complex ions, B...solution containing NH + 4 ions and F - ions, C... peeling process, D... crystallization process, E... Fluorometallic ammonium crystal, F
...Aqueous solution containing metal ions or metal complex ions, G...Extraction step. Note that the same reference numerals in each figure indicate the same or corresponding parts.
Claims (1)
の群、アルキルサルフアイドの群、カルボン酸の
群、オキシムの群、ケトンの群、中性燐酸エステ
ルの群、炭素数４〜25の高級アルコールの群、及
び第１級〜第４級アミンの各群から成る群から選
択された１種又は２種以上の抽出剤を石油系炭化
水素で希釈してなる有機溶媒に抽出含有されてい
るAg、Ｂ、Bi、Cr、Ir、Ga、Ge、Mn、Li、
Pb、Sb、Sn、Ti、Hf及びZrのイオン又はこれ
らの金属錯イオンの１種を含む有機溶媒と、F-
イオン及びNH+ 4イオンを含有する水溶液とを接
触させることにより、上記金属イオン又は金属錯
イオンを水相に移行させて、Ag、Ｂ、Bi、Cr、
Ir、Ga、Ge、Mn、Li、Pb、Sb、Sn、Ti、Hf及
びZrのフツ素含有金属アンモニウム塩を造ると
共に該有機溶媒を再生させることを特徴とするフ
ツ素含有金属アンモニウム塩の製造方法。1 Alkyl phosphoric acid group, alkyl/aryl phosphoric acid group, alkyl sulfide group, carboxylic acid group, oxime group, ketone group, neutral phosphoric ester group, higher alcohol group having 4 to 25 carbon atoms, Ag, B, Bi, Cr, Ir, Ga, Ge, Mn, Li,
an organic solvent containing Pb, Sb, Sn, Ti, Hf, and Zr ions or one of these metal complex ions, and F -
By bringing the metal ions or metal complex ions into contact with an aqueous solution containing ions and NH + 4 ions, the metal ions or metal complex ions are transferred to the aqueous phase to form Ag, B, Bi, Cr,
Production of a fluorine-containing metal ammonium salt of Ir, Ga, Ge, Mn, Li, Pb, Sb, Sn, Ti, Hf, and Zr, which is characterized by producing the fluorine-containing metal ammonium salt and regenerating the organic solvent. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17845384A JPS6158814A (en) | 1984-08-29 | 1984-08-29 | Method for producing fluorine-containing metal ammonium salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17845384A JPS6158814A (en) | 1984-08-29 | 1984-08-29 | Method for producing fluorine-containing metal ammonium salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6158814A JPS6158814A (en) | 1986-03-26 |
| JPH049734B2 true JPH049734B2 (en) | 1992-02-21 |
Family
ID=16048779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17845384A Granted JPS6158814A (en) | 1984-08-29 | 1984-08-29 | Method for producing fluorine-containing metal ammonium salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6158814A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5788948A (en) * | 1993-10-22 | 1998-08-04 | The University Of Melbourne | Process for the production of fluorometallate salts useful in the processing of mineral sands and related materials |
-
1984
- 1984-08-29 JP JP17845384A patent/JPS6158814A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6158814A (en) | 1986-03-26 |
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