JPS6120353B2 - - Google Patents
Info
- Publication number
- JPS6120353B2 JPS6120353B2 JP15073878A JP15073878A JPS6120353B2 JP S6120353 B2 JPS6120353 B2 JP S6120353B2 JP 15073878 A JP15073878 A JP 15073878A JP 15073878 A JP15073878 A JP 15073878A JP S6120353 B2 JPS6120353 B2 JP S6120353B2
- Authority
- JP
- Japan
- Prior art keywords
- aqueous phase
- alcohol
- phosphoric acid
- acidic
- ester
- 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
- 239000008346 aqueous phase Substances 0.000 claims description 30
- 230000002378 acidificating effect Effects 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 9
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- 238000000605 extraction Methods 0.000 description 10
- 150000002739 metals Chemical class 0.000 description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- -1 2 -ethylhexyl group Chemical group 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 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
- 238000000746 purification Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 2
- WFRBDWRZVBPBDO-UHFFFAOYSA-N 2-methyl-2-pentanol Chemical compound CCCC(C)(C)O WFRBDWRZVBPBDO-UHFFFAOYSA-N 0.000 description 2
- NGDNVOAEIVQRFH-UHFFFAOYSA-N 2-nonanol Chemical compound CCCCCCCC(C)O NGDNVOAEIVQRFH-UHFFFAOYSA-N 0.000 description 2
- GYSCXPVAKHVAAY-UHFFFAOYSA-N 3-Nonanol Chemical compound CCCCCCC(O)CC GYSCXPVAKHVAAY-UHFFFAOYSA-N 0.000 description 2
- IWTBVKIGCDZRPL-UHFFFAOYSA-N 3-methylpentanol Chemical compound CCC(C)CCO IWTBVKIGCDZRPL-UHFFFAOYSA-N 0.000 description 2
- YVBCULSIZWMTFY-UHFFFAOYSA-N 4-Heptanol Natural products CCCC(O)CCC YVBCULSIZWMTFY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 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
- 239000010452 phosphate Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000001618 (3R)-3-methylpentan-1-ol Substances 0.000 description 1
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- RFZHJHSNHYIRNE-UHFFFAOYSA-N 2,3-dimethylpentan-3-ol Chemical compound CCC(C)(O)C(C)C RFZHJHSNHYIRNE-UHFFFAOYSA-N 0.000 description 1
- FMLSQAUAAGVTJO-UHFFFAOYSA-N 2,4-dimethylpentan-2-ol Chemical compound CC(C)CC(C)(C)O FMLSQAUAAGVTJO-UHFFFAOYSA-N 0.000 description 1
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- NDVWOBYBJYUSMF-UHFFFAOYSA-N 2-methylcyclohexan-1-ol Chemical compound CC1CCCCC1O NDVWOBYBJYUSMF-UHFFFAOYSA-N 0.000 description 1
- LCFKURIJYIJNRU-UHFFFAOYSA-N 2-methylhexan-1-ol Chemical compound CCCCC(C)CO LCFKURIJYIJNRU-UHFFFAOYSA-N 0.000 description 1
- KBCNUEXDHWDIFX-UHFFFAOYSA-N 2-methyloctan-2-ol Chemical compound CCCCCCC(C)(C)O KBCNUEXDHWDIFX-UHFFFAOYSA-N 0.000 description 1
- RMBUNHOAKTUXTC-UHFFFAOYSA-N 3-ethyl-5-methylhexan-3-ol Chemical compound CCC(O)(CC)CC(C)C RMBUNHOAKTUXTC-UHFFFAOYSA-N 0.000 description 1
- WNDLTOTUHMHNOC-UHFFFAOYSA-N 3-ethylhexan-3-ol Chemical compound CCCC(O)(CC)CC WNDLTOTUHMHNOC-UHFFFAOYSA-N 0.000 description 1
- XKIRHOWVQWCYBT-UHFFFAOYSA-N 3-ethylpentan-3-ol Chemical compound CCC(O)(CC)CC XKIRHOWVQWCYBT-UHFFFAOYSA-N 0.000 description 1
- KYWJZCSJMOILIZ-UHFFFAOYSA-N 3-methylhexan-3-ol Chemical compound CCCC(C)(O)CC KYWJZCSJMOILIZ-UHFFFAOYSA-N 0.000 description 1
- DTDMYWXTWWFLGJ-JTQLQIEISA-N 4-Decanol Natural products CCCCCC[C@@H](O)CCC DTDMYWXTWWFLGJ-JTQLQIEISA-N 0.000 description 1
- GNROHGFUVTWFNG-UHFFFAOYSA-N 4-ethylheptan-4-ol Chemical compound CCCC(O)(CC)CCC GNROHGFUVTWFNG-UHFFFAOYSA-N 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- FBLFIHQPSPSEIA-UHFFFAOYSA-N 4-propylheptan-1-ol Chemical compound CCCC(CCC)CCCO FBLFIHQPSPSEIA-UHFFFAOYSA-N 0.000 description 1
- RGCZULIFYUPTAR-UHFFFAOYSA-N 5-Methylhexan-3-ol Chemical compound CCC(O)CC(C)C RGCZULIFYUPTAR-UHFFFAOYSA-N 0.000 description 1
- ZDVJGWXFXGJSIU-UHFFFAOYSA-N 5-methylhexan-2-ol Chemical compound CC(C)CCC(C)O ZDVJGWXFXGJSIU-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000007796 conventional method Methods 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
- DTDMYWXTWWFLGJ-UHFFFAOYSA-N decan-4-ol Chemical compound CCCCCCC(O)CCC DTDMYWXTWWFLGJ-UHFFFAOYSA-N 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
- 230000002349 favourable effect Effects 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 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
- 125000005425 toluyl group Chemical group 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Physical Water Treatments (AREA)
- Removal Of Specific Substances (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法
に関するものである。詳しくは本発明は、酸性リ
ン酸エステルを用いる金属の分離、精製などにお
いて得られる微量の酸性リン酸エステルが溶存す
る水相から、酸性リン酸エステルを析出させて除
去する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for removing acidic phosphate esters in an aqueous phase. Specifically, the present invention relates to a method for precipitating and removing acidic phosphoric ester from an aqueous phase in which trace amounts of acidic phosphoric ester are dissolved, which are obtained in the separation and purification of metals using acidic phosphoric ester.
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の分離、精
製を行う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 a solution thereof in an organic solvent 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
トリツピング剤、例えば鉱酸水溶液、キレート剤
水溶液などと接触させて金属を水相に移行させる
逆抽出工程を多段組合せて行う。 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 an extractant phase containing the metal and a stripping agent, such as an aqueous mineral acid solution. A multi-stage combination of back extraction steps is performed in which metals are brought into contact with an aqueous solution of a chelating agent and transferred to an aqueous phase.
上記逆抽出工程によつて金属を含有したストリ
ツピング剤水溶液からなる水相は、更に別の抽剤
による抽出などによつて金属を離脱し、逆抽出工
程に循環使用されるが、この水相に抽剤が残存す
ることは、逆抽出段に抽剤を持ち込むことになつ
て、抽出率の低下を招いたり、運転管理を難しく
するなどのおそれがある。 The aqueous phase consisting of the aqueous stripping agent solution containing metals in the above back-extraction process is further extracted with another extraction agent to remove the metals and recycled to the back-extraction process. If the extractant remains, the extractant will be brought into the back extraction stage, leading to a decrease in the extraction rate and making operation management difficult.
また、抽出工程において全金属を抽出した後の
廃水、あるいは抽剤の循環使用に際して抽剤を水
洗浄または酸洗浄した洗浄廃水のような廃水中に
抽剤が残存することは、廃水処理の負担を大きく
する。 In addition, the residual extractant in wastewater, such as wastewater after all metals have been extracted in the extraction process, or washing wastewater after washing the extractant with water or acid when recycling the extractant, is a burden on wastewater treatment. Make it bigger.
本発明者らは、上記のような酸性リン酸エステ
ル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
相と特定のアルコールとを接触させるときは、酸
性リン酸エステルのほとんどがアルコール相に移
行し、水相から容易に酸性リン酸エステルを除去
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 extensive research into methods for removing acidic phosphate esters from the aqueous phase containing the above-mentioned acidic phosphate esters. The present invention was completed based on the knowledge that most of the acidic phosphoric esters migrate to the alcohol phase and that the acidic phosphoric esters can be easily removed from the aqueous phase.
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
とするものであり、この目的は、酸性リン酸エス
テルを含有する水相と、水に難溶性で液状の脂肪
族または脂環式のアルコールとを接触させ、酸性
リン酸エステルをアルコール相に移行させて分離
することによつて達成される。 That is, an object of the present invention is to efficiently remove acidic phosphate esters in an aqueous phase by a simple means. This is achieved by contacting a soluble, liquid aliphatic or alicyclic alcohol and transferring the acidic phosphoric acid ester to the alcohol phase for separation.
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
ピル基、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 propyl group, a butyl group, a hexyl group, an octyl group, 2
-ethylhexyl group, decyl group, dodecyl group, octadecyl group, 7,7-dimethyl-2-(3',
Alkyl groups with a straight chain or side chain having 20 or less carbon atoms such as 3'-dimethyl-1'-methylbutyl)-5-methyloctyl group, aryl groups such as phenyl group and toluyl group, and cyclohexyl group. Examples include cycloalkyl groups such as cycloalkyl groups, and aralkyl groups such as benzyl groups.
本発明は例えば、ジ―（２―エチルヘキシル）
リン酸、モノオクチルリン酸、ジ―〔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、リン酸のモノ又はジ―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, for example, di-(2-ethylhexyl)
Monophosphoric acid, such as phosphoric acid, monooctyl phosphoric acid, di-[7,7-dimethyl-2-(3',3'-dimethyl-1'-methylbutyl)-5-methyloctyl] phosphoric acid, etc. Particularly favorable results can be obtained when the method is applied to the treatment of an aqueous phase containing a di-higher alkyl ester.
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
ピルエーテルのようなエーテル類、ニトロベンゼ
ン類などに溶解状態で、金属の抽剤として使用さ
れるものである。 The acidic phosphoric acid ester referred to in the present invention as described above may be used as it is, or in order to reduce the viscosity, it may be mixed with an organic solvent that is sparingly soluble in water, such as kerosene, hexane,
It is used as a metal extractant when dissolved in hydrocarbons such as benzene, toluene, and xylene, ethers such as ethyl ether, butyl ether, and isopropyl ether, and nitrobenzenes.
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、金属の塩の水溶性と上記した
抽剤とを接触させて全金属を抽剤相に移行させた
後分液して得た水相、金属を脱離後のストリツピ
ング剤水溶液からなる水相、あるいは、金属の分
離、精製工程から排出される廃水などがあげられ
るが、これに限られるものではなく、酸性リン酸
エステルを溶解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 can be obtained by bringing a water-soluble metal salt into contact with the above-mentioned extractant to transfer all the metals to the extractant phase, and then separating the liquid. Examples include, but are not limited to, an aqueous phase consisting of an aqueous solution of a stripping agent after removing metals, or waste water discharged from metal separation and purification processes. Any aqueous phase contained in dissolved or mist form can be targeted.
本発明で使用する水に難溶性で液状の脂肪族ま
たは脂環式のアルコールとしては、水に対する溶
解度が常温付近で２重量％以下、好ましくは１重
量％以下であり、常温付近で液状のものである。
水に対する溶解度が大きいと、酸性リン酸エステ
ルはアルコールに移行するけれども、酸性リン酸
エステルを含有するアルコールが水相中に残るた
めに、水相から酸性リン酸エステルを除去すると
いう効果が小さくなり、加えて、この水相を更に
別の抽出工程に供給する場合には、別の抽出工程
にアルコールを持ち込むことになつて好ましくな
い。 The liquid aliphatic or alicyclic alcohol that is sparingly soluble in water used in the present invention has a solubility in water of 2% by weight or less, preferably 1% by weight or less at around room temperature, and is liquid at around room temperature. It is.
If the solubility in water is high, the acidic phosphoric ester will transfer to alcohol, but the alcohol containing the acidic phosphoric ester will remain in the aqueous phase, making it less effective in removing the acidic phosphoric ester from the aqueous phase. In addition, when this aqueous phase is further supplied to another extraction step, alcohol is brought into the other extraction step, which is undesirable.
本発明で使用するのに好適なアルコールの具体
例としては、１―ヘキサノール、２―エチル―１
―ブタノール、３―メチル―１―ペンタノール、
１―ヘプタノール、２―ヘプタノール、４―ヘプ
タノール、２，４―ジメチル―２―ペンタノー
ル、２，３―ジメチル―３―ペンタノール、３―
エチル―３―ペンタノール、２―メチル―１―ヘ
キサノール、５―メチル―２―ヘキサノール、３
―メチル―３―ヘキサノール、５―メチル―３―
ヘキサノール、１―オクタノール、２―オクタノ
ール、２―エチル―１―ヘキサノール、３―エチ
ル―３―ヘキサノール、２―メチル―２―ペンタ
ノール、１―ノナノール、２―ノナノール、３―
ノナノール、３―エチル―５―メチル―３―ヘキ
サノール、４―エチル―４―ヘプタノール、２―
メチル―２―オクタノール、４―デカノール、４
―プロピル―４―ヘプタノールのような脂肪族ア
ルコール、２―メチルシクロヘキサノール、３―
メチルシクロヘキサノールのような脂環式アルコ
ールなどの、炭素数６〜10の一価アルコールがあ
げられるが、水に難溶で且つ液状であれば、これ
らに限定されるものではない。 Specific examples of alcohols suitable for use in the present invention include 1-hexanol, 2-ethyl-1
-butanol, 3-methyl-1-pentanol,
1-heptanol, 2-heptanol, 4-heptanol, 2,4-dimethyl-2-pentanol, 2,3-dimethyl-3-pentanol, 3-
Ethyl-3-pentanol, 2-methyl-1-hexanol, 5-methyl-2-hexanol, 3
-Methyl-3-hexanol, 5-methyl-3-
Hexanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 3-ethyl-3-hexanol, 2-methyl-2-pentanol, 1-nonanol, 2-nonanol, 3-
Nonanol, 3-ethyl-5-methyl-3-hexanol, 4-ethyl-4-heptanol, 2-
Methyl-2-octanol, 4-decanol, 4
-Aliphatic alcohols such as propyl-4-heptanol, 2-methylcyclohexanol, 3-
Examples include monohydric alcohols having 6 to 10 carbon atoms, such as alicyclic alcohols such as methylcyclohexanol, but are not limited to these as long as they are poorly soluble in water and are liquid.
これらアルコールは単独でまたは混合して用い
ることができ、混合アルコールの場合は、液状で
水に難溶性である限り、上に例示した以外のアル
コールを含有していてもよい。 These alcohols can be used alone or in combination, and in the case of mixed alcohols, alcohols other than those exemplified above may be contained as long as they are liquid and poorly soluble in water.
上記アルコールの使用量は、酸性リン酸エステ
ルを移行させる目的からは、多く用いるのが好ま
しいけれども、経済性、操作の容易さ、装置の大
きさなどを考慮すると、水相に対して0.1〜10容
量倍、好ましくは0.2〜５容量倍程度を用いるの
がよい。 Although it is preferable to use a large amount of alcohol for the purpose of transferring the acidic phosphate ester, considering economic efficiency, ease of operation, size of the device, etc., the amount of alcohol used is 0.1 to 10 It is preferable to use a volume double, preferably about 0.2 to 5 times the volume.
水相と上記アルコールとの接触は、通常採用さ
れる液―液の混合方法で十分であり、例えば撹拌
槽を用いて両者を混合する方法が適用できる。接
触の時間は、含有成分の種類、濃度などによつて
差はあるが、撹拌槽を用いる場合、通常５〜20分
間程度で十分である。 For the contact between the aqueous phase and the alcohol, a commonly employed liquid-liquid mixing method is sufficient, and for example, a method of mixing the two using a stirring tank can be applied. The contact time varies depending on the type and concentration of the components contained, but when a stirring tank is used, about 5 to 20 minutes is usually sufficient.
接触を行う際の水相のpHは、特特に影響はな
いので、任意のpHで行うことができる。また、
温度は、常温以外の温度を選ぶこともできるが、
通常常温付近で十分である。 The pH of the aqueous phase at the time of contacting has no particular influence, so the contacting can be carried out at any pH. Also,
You can choose a temperature other than room temperature, but
Usually around room temperature is sufficient.
かくして、水相と上記アルコールとを接触させ
ると、水相中の酸性リン酸エステルは、そのほと
んどがアルコール相に移行し、水相中の残存酸性
リン酸エステルの量を、水相に対して数ppm以
下とすることができる。 Thus, when the aqueous phase and the alcohol are brought into contact, most of the acidic phosphoric ester in the aqueous phase transfers to the alcohol phase, and the amount of the remaining acidic phosphoric ester in the aqueous phase is reduced relative to the aqueous phase. It can be several ppm or less.
上記接触を行つた後は、静置するのみで水相と
脂肪族アルコール相に分離するので、常法に従つ
て分液を行えばよい。 After the above-mentioned contact has been carried out, the mixture can be separated into an aqueous phase and an aliphatic alcohol phase simply by allowing it to stand still, so liquid separation can be carried out according to a conventional method.
また、充填塔、多段塔、あるいは撹拌機付の塔
などを用い、水相と脂肪族アルコールとを向流で
供給することにより、両者の接触と分液を行うこ
ともできる。 Furthermore, by using a packed tower, a multistage tower, a tower equipped with a stirrer, or the like, and supplying the aqueous phase and the aliphatic alcohol in countercurrent flow, contact and liquid separation between the two can be performed.
本発明方法によるときは、容易な操作で効率よ
く、水相中の酸性リン酸エステルを除去できるの
で、工業的価値が大きい。 The method of the present invention has great industrial value because the acidic phosphate ester in the aqueous phase can be removed efficiently with easy operation.
以下、実施例によつて本発明を更に具体的に説
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。 Hereinafter, the present invention will be explained in more detail 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
ジ―〔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100mlを、0.1N硝酸20mlと共に分液ロートに
入れ、30秒間振盪して酸洗浄を行い、静置後分液
した。Example 1 100 ml of di-[7.7-dimethyl-2-(3',3'-dimethyl-1'-methylbutyl)-5-methyloctyl]phosphoric acid was placed in a separating funnel with 20 ml of 0.1N nitric acid, and the mixture was stirred for 30 seconds. Acid washing was performed by shaking, and the liquid was separated after being allowed to stand still.
分液して得た水相中のジ―〔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〕リン酸の量は、ミス
ト状のものも合せて1000ppmであつた。 The amount of di-[7,7-dimethyl-2-(3',3'-dimethyl-(1-methylbutyl)-5-methyloctyl) phosphoric acid in the aqueous phase obtained by separation is The total amount was 1000ppm.
この水相に、２―エチルヘキサノール100mlを
加え、分液ロートを用いて５分間振盪後、静置し
て分液した。 To this aqueous phase, 100 ml of 2-ethylhexanol was added, and after shaking for 5 minutes using a separating funnel, the mixture was allowed to stand still to separate the layers.
得られた水相中のジ―〔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〕リン酸の量は、3.0ppmであ
つた。 Di-[7,7-dimethyl-2 in the obtained aqueous phase
-(3',3'-dimethyl-1-methylbutyl)-5
The amount of -methyloctyl]phosphoric acid was 3.0 ppm.
実施例 ２
ジ―（２―エチルヘキシル）リン酸の１モル／
ケロシン溶液100mlを、水100mlと共に分液ロー
トに入れ、１分間振盪して水洗を行い、静置後分
液した。Example 2 1 mole of di-(2-ethylhexyl)phosphoric acid/
100 ml of the kerosene solution was put into a separating funnel along with 100 ml of water, shaken for 1 minute to wash with water, and then allowed to stand still for separation.
分液して得た水相中のジ―（２―エチルヘキシ
ル）リン酸の量は、ミスト状のものも含めて
500ppmであつた。 The amount of di-(2-ethylhexyl) phosphoric acid in the aqueous phase obtained by separation, including that in the form of mist,
It was 500ppm.
この水相に１―ヘキサノール100mlを加え、分
液ロートを用いて５分間振盪後、静置して分液し
た。 100 ml of 1-hexanol was added to this aqueous phase, and after shaking for 5 minutes using a separating funnel, the mixture was allowed to stand to separate the layers.
得られた水相中のジ―（２―エチルヘキシル）
リン酸の量は、2.8ppmであつた。 Di-(2-ethylhexyl) in the resulting aqueous phase
The amount of phosphoric acid was 2.8 ppm.
Claims (1)
難溶性で液状の脂肪族または脂環式アルコールと
を接触させ、酸性リン酸エステルをアルコール相
に移行させて分離す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法。1. Water characterized by contacting an aqueous phase containing an acidic phosphoric ester with a liquid aliphatic or alicyclic alcohol that is poorly soluble in water, and transferring the acidic phosphoric ester to the alcohol phase for separation. Method for removing acidic phosphate esters in phases.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15073878A JPS5575783A (en) | 1978-12-06 | 1978-12-06 | Removing method of acidic phosphate in aqueous phase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15073878A JPS5575783A (en) | 1978-12-06 | 1978-12-06 | Removing method of acidic phosphate in aqueous phase |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5575783A JPS5575783A (en) | 1980-06-07 |
| JPS6120353B2 true JPS6120353B2 (en) | 1986-05-21 |
Family
ID=15503325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15073878A Granted JPS5575783A (en) | 1978-12-06 | 1978-12-06 | Removing method of acidic phosphate in aqueous phase |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5575783A (en) |
-
1978
- 1978-12-06 JP JP15073878A patent/JPS5575783A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5575783A (en) | 1980-06-07 |
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