JPS5814828B2 - Method for removing acidic phosphate esters in aqueous phase - Google Patents
Method for removing acidic phosphate esters in aqueous phaseInfo
- Publication number
- JPS5814828B2 JPS5814828B2 JP53124480A JP12448078A JPS5814828B2 JP S5814828 B2 JPS5814828 B2 JP S5814828B2 JP 53124480 A JP53124480 A JP 53124480A JP 12448078 A JP12448078 A JP 12448078A JP S5814828 B2 JPS5814828 B2 JP S5814828B2
- Authority
- JP
- Japan
- Prior art keywords
- aqueous phase
- acidic phosphate
- phosphoric acid
- acidic
- water
- 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
Links
- 230000002378 acidificating effect Effects 0.000 title claims description 32
- 239000008346 aqueous phase Substances 0.000 title claims description 29
- 150000003014 phosphoric acid esters Chemical class 0.000 title claims description 16
- 238000000034 method Methods 0.000 title description 9
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- -1 phosphate ester Chemical class 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- 239000010452 phosphate Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 238000000605 extraction Methods 0.000 description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Removal Of Specific Substances (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
【発明の詳細な説明】
本発明は、水相中の酸性リン酸エステルの除去力法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for removing acidic phosphate esters in an aqueous phase.
詳しくは、酸性リン酸エステルおよび水溶性の多価金属
塩を含有する水相から、酸性リン酸エステルを涙過し得
る固体として析出させて除去する方法に関するものであ
る。Specifically, the present invention relates to a method for precipitating and removing an acidic phosphoric acid ester as a washable solid from an aqueous phase containing the acidic phosphoric acid ester and a water-soluble polyvalent metal salt.
ジー（２−エチルヘキシル）リン酸のような酸性リン酸
エステル、または、その有機溶媒溶液を抽剤として用い
、希土類金属その他の金属を分離、精製する方法は広く
行われている。BACKGROUND ART A method of separating and purifying rare earth metals and other metals using an acidic phosphoric acid ester such as di(2-ethylhexyl) phosphoric acid or an organic solvent solution thereof as an extractant is widely used.
抽剤を用いる金属の分離、精製は、通常、金属塩水溶液
と抽剤とを接触させて金属を抽剤相に移行させる抽出工
程、および、金属を含有する抽剤相とス｝Ｊツピング剤
、例えば鉱酸水溶液やキレート剤水溶液などとを接触さ
せて、金属を水相であるストリツピング剤相に移行させ
る逆抽出工程を組合せて行う。Separation and purification of metals using an extractant usually involves an extraction process in which an aqueous metal salt solution and an extractant are brought into contact to transfer the metal to an extractant phase, and the extractant phase containing the metal is transferred to an extraction agent. This is carried out in combination with a back extraction step in which the metal is transferred to a stripping agent phase, which is an aqueous phase, by bringing the metal into contact with, for example, an aqueous mineral acid solution or an aqueous chelating agent solution.
上記抽剤として使用されるジー（２−エチルヘキシル）
リン酸のような酸性リン酸エステルは、水に難溶性であ
り、水相中への混入は少いけれども、上記逆抽出工程で
得られる水相は、製品である金属を含有するので、この
中に酸性リン酸エステルが残存すると、製品中にリン分
が不純物として混入することになって好ましくない。Di(2-ethylhexyl) used as the above extractant
Acidic phosphoric acid esters such as phosphoric acid are poorly soluble in water and are rarely mixed into the aqueous phase, but since the aqueous phase obtained in the above back extraction process contains metal products, this If acidic phosphate ester remains in the product, phosphorus will be mixed into the product as an impurity, which is undesirable.
また、上記抽出工程で得られる水相は、抽出挙動の異な
る抽剤を用いる別の抽出工程に導いて、上記抽出工程に
おけるとは別の金属の抽出を行うことがあるが、この水
相中に抽剤が残存することは、別の抽出段に抽剤を持ち
込むことになって、抽出率の低下を招いたり、運転管理
を難しくするおそれがあって好ましくない。In addition, the aqueous phase obtained in the above extraction step may be led to another extraction step using an extractant with a different extraction behavior to extract a different metal from that in the above extraction step. It is undesirable for the extraction agent to remain in the extraction stage, since the extraction agent will be brought into another extraction stage, leading to a decrease in the extraction rate and making operation management difficult.
本発明者らは、上記の工程で得られるような酸性リン酸
エステルおよび水溶性の多価金属塩を含有する水相から
、酸性リン酸エステルを除去する方法につき、鋭意研究
を重ねた結果、上記水相にアルカリを添加してｐＨを調
整するときは、酸性リン酸エステルを含有する固体が析
出し、ろ過などによって容易に除去することが、できる
ことを知得して本発明を完成した。The present inventors have conducted intensive research on a method for removing acidic phosphoric esters from the aqueous phase containing acidic phosphoric esters and water-soluble polyvalent metal salts as obtained in the above steps. The present invention was completed based on the knowledge that when an alkali is added to the aqueous phase to adjust the pH, a solid containing an acidic phosphate ester precipitates and can be easily removed by filtration or the like.
すなわち本発明は、水相中の酸性リン酸エステルを容易
な手段で効率よく除去することを目的と１するものであ
り、この目的は、酸性リン酸エステルおよび水溶性の多
価金属塩を含有する水相に、アルカリを添加してｐＨを
調整し、酸性リン酸エステル含有固体を析出させること
によって達成される。That is, an object of the present invention is to efficiently remove acidic phosphate esters in an aqueous phase by easy means. This is achieved by adding an alkali to the aqueous phase to adjust the pH and precipitating the acidic phosphate ester-containing solid.
以下、本発明を詳細に説明する。The present invention will be explained in detail below.
本発明でいう酸性リン酸エステルとは、有機基１個また
は２個を有するリン酸のエステルであり、有機基として
は、メチル基、エチル基、プロビル基、ブチル基、ヘキ
シル基、オクチル基、２−エチルヘキシル基、デシル基
、ドデシル基、オクタデシル基、７，７−ジメチル−２
−（３’，３’−ジメチル−１′−メチルブチル）−５
−メチルオクチル基などのような炭素数２０以下の直鎖
または側鎖を有するアルキル基、フエニル基、トルイル
基のようなアリール基、シクロヘキシル基のようなシク
ロアルキル基、ベンジル基のようなアラルキル基などが
あげられる。The acidic phosphoric acid ester in the present invention is an ester of phosphoric acid having one or two organic groups, and examples of the organic group include a methyl group, an ethyl group, a probyl group, a butyl group, a hexyl group, an octyl group, 2-ethylhexyl group, decyl group, dodecyl group, octadecyl group, 7,7-dimethyl-2
-(3',3'-dimethyl-1'-methylbutyl)-5
- Alkyl groups with a straight chain or side chain of up to 20 carbon atoms such as methyloctyl, aryl groups such as phenyl and tolyl, cycloalkyl groups such as cyclohexyl, and aralkyl groups such as benzyl etc.
本発明は、例えば、ジー（２−エチルヘキシノレ）リン
酸、モノオクチルリン酸、ジー〔７，７−ジメチル−２
−（３’，３’−ジメチル−１′−メチルブチル）−５
−メチルオクチル〕リン酸などのような、リン酸のモノ
またはジー高級アルキルエステルを含有する水相の処理
に適用すると、特に好ましい結果が得られる。The present invention can be applied, for example, to di(2-ethylhexynole) phosphoric acid, monooctyl phosphoric acid, di[7,7-dimethyl-2
-(3',3'-dimethyl-1'-methylbutyl)-5
Particularly favorable results are obtained when applied to the treatment of aqueous phases containing mono- or di-higher alkyl esters of phosphoric acid, such as -methyloctyl]phosphoric acid and the like.
上記のような本発明でいう酸性リン酸エステルは、その
まま、または粘度を低下させるため水に難溶性の有機溶
媒、例えばケロシン、ヘキサン、ベンゼン、トルエン、
キシレンのような炭化水素類、エチルエーテル、ブチル
エーテル、イソプロビルエーテルのようなエーテル類、
ニトロベンゼン類などに溶解して抽剤として使用される
ものである。The acidic phosphoric acid ester referred to in the present invention as mentioned above can be used as it is or in order to reduce the viscosity, it can be used in organic solvents that are sparingly soluble in water, such as kerosene, hexane, benzene, toluene,
Hydrocarbons such as xylene, ethers such as ethyl ether, butyl ether, isopropyl ether,
It is used as an extractant by dissolving it in nitrobenzenes, etc.
本発明で対象とする酸性リン酸エステルを含有する水相
としては、金属の塩の水溶液と上記した抽剤とを接触さ
せて金属を抽剤相に移行させた後分液して得た水相、あ
るい；バ金属を含有する抽剤とストリツピング剤水溶液
を接触させて、金属を塩の形で水相に逆抽出した後、分
液して得た水相などがあげられるが、これらに限られる
ものではなく、酸性リン酸エステルおよび水溶性の多価
金属塩を溶解またはスラリー状もしくはミスト状で含有
している水相は何れも対象とすることができる。The aqueous phase containing the acidic phosphoric acid ester targeted in the present invention is water obtained by contacting an aqueous solution of a metal salt with the above extractant to transfer the metal to the extractant phase, and then separating the liquid. phase, or; an aqueous phase obtained by contacting an extractant containing a metal with an aqueous solution of a stripping agent, back-extracting the metal in the form of a salt into the aqueous phase, and then separating the liquids. However, any aqueous phase containing an acidic phosphoric acid ester and a water-soluble polyvalent metal salt in the form of a solution, slurry, or mist can be used.
本発明方法においては、酸性リン酸エステルおよび水溶
性の多価金属塩を含有する水相に、アルカリを添加して
ｐｉ｛を調整するが、アルカリとじては、アンモニア、
水酸化ナｌ− ＩＪウム、水酸化カリウムのような苛性
アルカリ、炭酸ナ｝ＩＪウム、炭酸カリウムのような炭
酸アルカリなどがあげられる。In the method of the present invention, an alkali is added to an aqueous phase containing an acidic phosphoric acid ester and a water-soluble polyvalent metal salt to adjust pi{.
Examples include caustic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, and alkali carbonates such as potassium carbonate.
ｐＨの調整の程度は、水相中に含有されている酸性リン
酸エステルの種類によって好適な価が異なるので、酸性
リン酸エステル含有固体の析出が十分に起るように適宜
選択するのがよい。The degree of pH adjustment varies depending on the type of acidic phosphate ester contained in the aqueous phase, so it is best to select it appropriately so that precipitation of the acidic phosphate-containing solid occurs sufficiently. .
例えば、ジ−（２−エチルヘキシル）リン酸の場合１ｔ
＊、ｐＨ０．５以上、好ましくはｐＨ１．０以上とする
のがよく、ジー〔７，７−ジメチル−２−（３’，３’
−ジメチル−１′−メチルブチル）−５−メチルオクチ
ル〕リン酸の場合は、ｐＨ５以上、好ましくはｐ｝Ｔ６
以上とするのがよい。For example, in the case of di-(2-ethylhexyl) phosphoric acid, 1t
*, pH 0.5 or higher, preferably pH 1.0 or higher, and di[7,7-dimethyl-2-(3',3'
-dimethyl-1'-methylbutyl)-5-methyloctyl]phosphoric acid, pH 5 or higher, preferably p}T6
It is better to set it to the above.
一般に、炭素数が大きく、また側鎖が多いアルキル基を
有する酸性リン酸エステルは、ｐＨを高くすることが望
ましい傾向があるが、通常，ｐＨを６以上とすれば十分
である。In general, acidic phosphoric acid esters having a large number of carbon atoms and an alkyl group with many side chains tend to have a high pH, but it is usually sufficient to have a pH of 6 or higher.
本発明方法を実施するには、酸性リン酸エステルおよび
水溶性の多価金属塩を含有する水相に、所要量の上記ア
ルカリを添加して攪拌するのみで、酸性リン酸エステル
含有固体が析出するので、該析出物を炉過などの手段で
分離すればよい。To carry out the method of the present invention, the solid containing the acidic phosphate ester is precipitated by simply adding the required amount of the above alkali to the aqueous phase containing the acidic phosphate ester and the water-soluble polyvalent metal salt and stirring. Therefore, the precipitate may be separated by means such as filtration.
本発明力法によって析出する酸性リン酸エステル含有固
体の組成は十分明らかではないが、酸性リン酸エステル
と多価金属からなる重合体と考えられる。Although the composition of the acidic phosphate ester-containing solid precipitated by the method of the present invention is not fully clear, it is thought to be a polymer consisting of an acidic phosphate ester and a polyvalent metal.
前記した抽出工程または逆抽出工程から得られる水相は
、通常、上記酸性リン酸エステルをほぼ完全に除去する
のに十分な量の水溶性の多価金属塩を含有しているが、
水相中の水溶性の多価金属塩の量が少ない場合には、そ
の水溶性の多価金属塩の量に相当する量の酸性リン酸エ
ステル含有固体しか析出させることができず、酸性リン
酸エステルの除去効果が不十分となるので、このような
場合には更に、水溶性の多価金属塩を添加するのがよい
。The aqueous phase obtained from the above-mentioned extraction step or back-extraction step usually contains a sufficient amount of water-soluble polyvalent metal salt to almost completely remove the acidic phosphate ester,
When the amount of water-soluble polyvalent metal salt in the aqueous phase is small, only the amount of acidic phosphate-containing solid that corresponds to the amount of water-soluble polyvalent metal salt can be precipitated, and In such cases, it is preferable to further add a water-soluble polyvalent metal salt since the acid ester removal effect becomes insufficient.
水溶性の多価金属塩としては、カルシウム、亜鉛、ガリ
ウム、イソジウム、イットリウム、チタニウム、ジルコ
ニウム、ハフニウム、錫、ニオフ、アンチモン、ビスマ
ス、モリブテン、鉄、セリウ１ム、サマリウム、ユーロ
ピウム、テルビラム、ツリウム、イツテルビウムのよう
なランタニド類金属、トリウム、ウランのようなアクチ
ニド類金属などの鉱酸塩、例えば塩化物、硝酸塩、硫酸
塩などがあげられる．
これらの水溶性の多価金属塩は、水溶液、水スラリー、
あるいは粉末など何れの形で加えてもよい。Water-soluble polyvalent metal salts include calcium, zinc, gallium, isodium, yttrium, titanium, zirconium, hafnium, tin, nioff, antimony, bismuth, molybdenum, iron, cerium, samarium, europium, terbilum, thulium, Examples include mineral acid salts of lanthanide metals such as ytterbium, actinide metals such as thorium and uranium, such as chlorides, nitrates, and sulfates. These water-soluble polyvalent metal salts can be used in aqueous solutions, aqueous slurries,
Alternatively, it may be added in any form such as powder.
また、添加量は特に制限はなく、飽和濃度もしくはそれ
以上であっても差し支えはないが、次段の抽出への影響
、経済的な理由などから、酸性リン酸エステルに対して
数百倍当量以下とするのがよい。In addition, there is no particular restriction on the amount added, and it may be at the saturation concentration or higher, but for reasons such as the effect on the next stage of extraction and for economical reasons, the addition amount should be several hundred times equivalent to the acidic phosphate ester. The following should be used.
本発明方法によるときは、簡単な操作によって、水相中
の酸性リン酸エステルを大巾に減少させることができ、
金属の抽出を多段で行う場合の水相の循環において、段
間の抽剤の混入を防止することが可能となって安定した
運転が容易となる、製品中への不純物が減少する、更に
は廃水中の酸性リン酸エステルを低減することができる
ので水処理の負担が軽くなる等、工業上多くの利益をあ
げることができるので、その価値は大きい。When using the method of the present invention, acidic phosphate esters in the aqueous phase can be greatly reduced by simple operations,
In the circulation of the aqueous phase when metal extraction is performed in multiple stages, it is possible to prevent the extraction agent from mixing between the stages, facilitating stable operation, reducing impurities in the product, and It is of great value because it can reduce the amount of acidic phosphate esters in wastewater, lightening the burden of water treatment, and yielding many industrial benefits.
以下、実施例によって本発明を具体的に説明するが、本
発明はその要旨をこえない限り以下の実施例に限定され
るものではない。EXAMPLES The present invention will be specifically explained below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.
実施例 １
塩化ランタンの０．２ｍｏｌ／ｌ 水溶液１００ｍｌと
、抽剤としてジー（２−エチルヘキシル）リン酸（Ｄ２
ＥＨＰＡ）の１ｍｏ１／ｌケロシン溶液１００ｍｌを
分液ロートに入れ、５分間振盪してランタンを抽剤相に
移行させ、抽剤相と水相に分液した。Example 1 100 ml of a 0.2 mol/l aqueous solution of lanthanum chloride and di(2-ethylhexyl) phosphoric acid (D2
100 ml of a 1 mol/l kerosene solution (EHPA) was placed in a separating funnel and shaken for 5 minutes to transfer the lanthanum to the extractant phase, which was then separated into an extractant phase and an aqueous phase.
水相のｐＨは０であり、水相中のＤ ２ ＥＨＰＡを測
定したところ、溶解しているものとミスト状になってい
るものと合せて３５０ｐ１）ｍであり、塩化ランタン０
．０ １ｍｏＩ／１４を含有していた。The pH of the aqueous phase was 0, and when D 2 EHPA in the aqueous phase was measured, the total amount of dissolved and mist-like D 2 EHPA was 350 p1) m, and lanthanum chloride was 0.
．． It contained 0 1mol/14.
この水相に５％アンモニア水を添加しｐＨを４としたと
ころ、白色の固形物が析出した。When 5% aqueous ammonia was added to this aqueous phase to adjust the pH to 4, a white solid was precipitated.
この析出物を５Ａのろ紙（東洋ろ紙■製）でろ過して得
た水相中のＤ２．ＥＨＰＡの量は３．８ｐｐｍであった
。The D2. The amount of EHPA was 3.8 ppm.
Claims (1)
有する水相に、アルカリを添加してｐＨを調整すること
により、酸性リン酸エステル含有固体を析出させること
を特徴とする水相中の酸性リン酸エステルの除去方法。1. An aqueous phase containing an acidic phosphate ester and a water-soluble polyvalent metal salt, which is characterized by adding an alkali to the aqueous phase to adjust the pH to precipitate an acidic phosphate-containing solid. How to remove acidic phosphate esters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53124480A JPS5814828B2 (en) | 1978-10-09 | 1978-10-09 | Method for removing acidic phosphate esters in aqueous phase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53124480A JPS5814828B2 (en) | 1978-10-09 | 1978-10-09 | Method for removing acidic phosphate esters in aqueous phase |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5551489A JPS5551489A (en) | 1980-04-15 |
| JPS5814828B2 true JPS5814828B2 (en) | 1983-03-22 |
Family
ID=14886554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP53124480A Expired JPS5814828B2 (en) | 1978-10-09 | 1978-10-09 | Method for removing acidic phosphate esters in aqueous phase |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5814828B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015087845A1 (en) * | 2013-12-13 | 2015-06-18 | 独立行政法人産業技術総合研究所 | Method for fractional precipitation of rare metal in aqueous system utilizing coordination polymerization |
| CN104556338A (en) * | 2014-12-04 | 2015-04-29 | 常州大学 | Phosphate blockade and restoration method for underground water in chemically polluted site |
-
1978
- 1978-10-09 JP JP53124480A patent/JPS5814828B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5551489A (en) | 1980-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| FI64792B (en) | FOERFARANDE FOER BEHANDLING AV BLANDNINGAR AV OXIDER AV SAELLSYNTA JORDMETALLER OCH GALLIUM | |
| CN106521190B (en) | The phosphine of neutrality containing amino extractant is used for the purposes and method of extracting and separating zirconium and/or hafnium | |
| RU2538863C2 (en) | Re-extraction method of rare-earth metals from organic solutions and obtainment of concentrate from rare-earth metals | |
| AU2012330712B2 (en) | Processes for metal ions removal of from aqueous solutions | |
| Preston et al. | The recovery of rare earth oxides from a phosphoric acid by-product. Part 2: The preparation of high-purity cerium dioxide and recovery of a heavy rare earth oxide concentrate | |
| US3586477A (en) | Removal of ferric iron from aqueous solutions of aluminum salts | |
| CN118103533A (en) | A green method for extracting lanthanides | |
| JP5299914B2 (en) | Extraction and separation method of rare earth elements | |
| MX2011005983A (en) | Method for extracting zinc from aqueous ammoniacal solutions. | |
| JPS5814828B2 (en) | Method for removing acidic phosphate esters in aqueous phase | |
| US3700415A (en) | Vanadium recovery from wet process phosphoric acid using neutral organophosphorus extractants | |
| JP4540738B1 (en) | Regeneration method of aqueous rust remover | |
| JPH0466816B2 (en) | ||
| JPS634028A (en) | How to treat scrap containing rare earths and iron | |
| EP0189831B1 (en) | Cobalt recovery method | |
| US3641226A (en) | Method for purification of di-(2-ethyl-hexyl) phosphoric acid | |
| JPH01249624A (en) | Treatment of residue containing rare earth element and cobalt | |
| JPS5814827B2 (en) | Method for removing acidic phosphate esters in aqueous phase | |
| JPS6037059B2 (en) | Method for purifying gallium solutions by liquid-liquid extraction with quaternary ammonium salts | |
| CN119194123B (en) | Organic phase regeneration method for poisoning by radioactive elements in rare earth smelting separation process | |
| SU945246A1 (en) | Method for recovering oxalic acid from waste pickling liquor | |
| AU2024364460A1 (en) | Method for removing the actinium contained in a rare earth solution with an organophosphorus solvent, and rare earth compositions obtained by this method | |
| JPS643551B2 (en) | ||
| JPS6120353B2 (en) | ||
| FR3154393A1 (en) | RARE EARTH COMPOSITION FROM LIQUID/LIQUID EXTRACTION OF SOLUTIONS FROM THE PROCESSING OF XENOTIME, MONAZITE, BASTNAESITE AND/OR IONIC CLAY ORES |