JP2024078487A - Removal method for removing organic impurity from organic solvent containing impurity - Google Patents
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- 239000012535 impurity Substances 0.000 title claims abstract description 164
- 239000003960 organic solvent Substances 0.000 title claims abstract description 146
- 238000000034 method Methods 0.000 title claims abstract description 107
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 151
- 238000005406 washing Methods 0.000 claims abstract description 110
- 239000007788 liquid Substances 0.000 claims abstract description 107
- 238000004090 dissolution Methods 0.000 claims abstract description 34
- 239000012074 organic phase Substances 0.000 claims abstract description 31
- 230000006866 deterioration Effects 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 24
- 239000003513 alkali Substances 0.000 claims abstract description 20
- 239000008346 aqueous phase Substances 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 17
- 238000011156 evaluation Methods 0.000 claims abstract description 14
- 229920002472 Starch Polymers 0.000 claims abstract description 11
- 235000019698 starch Nutrition 0.000 claims abstract description 11
- 239000008107 starch Substances 0.000 claims abstract description 11
- 239000013049 sediment Substances 0.000 claims description 90
- 238000000926 separation method Methods 0.000 claims description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 44
- 239000011701 zinc Substances 0.000 claims description 42
- 229910052725 zinc Inorganic materials 0.000 claims description 42
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 41
- 238000000605 extraction Methods 0.000 claims description 36
- 229910017052 cobalt Inorganic materials 0.000 claims description 26
- 239000010941 cobalt Substances 0.000 claims description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- 238000000638 solvent extraction Methods 0.000 claims description 19
- 238000002386 leaching Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 4
- 239000012044 organic layer Substances 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 22
- 239000000243 solution Substances 0.000 description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 36
- 229910052751 metal Inorganic materials 0.000 description 29
- 239000002184 metal Substances 0.000 description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000005416 organic matter Substances 0.000 description 19
- 229910052742 iron Inorganic materials 0.000 description 18
- 238000011282 treatment Methods 0.000 description 17
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 12
- 238000006386 neutralization reaction Methods 0.000 description 12
- 239000010949 copper Substances 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 238000003723 Smelting Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- UXGBMFKPXSGANM-UHFFFAOYSA-N 2,3,4,5-tetrachlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(Cl)=C(Cl)C(Cl)=C1Cl UXGBMFKPXSGANM-UHFFFAOYSA-N 0.000 description 4
- -1 compound salt Chemical class 0.000 description 4
- VYGSFTVYZHNGBU-UHFFFAOYSA-N trichloromethanesulfonic acid Chemical compound OS(=O)(=O)C(Cl)(Cl)Cl VYGSFTVYZHNGBU-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000001309 chloro group Chemical class Cl* 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000012854 evaluation process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000010888 waste organic solvent Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
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- 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
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- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
本発明は、不純物を含む有機溶媒から有機系不純物を除去する除去方法に関する。 The present invention relates to a method for removing organic impurities from an organic solvent containing impurities.
ニッケルやコバルトを含有する酸化鉱石からニッケルやコバルトを回収する方法の一つとして、酸化鉱石を硫酸溶液と共に２００℃を超える高温高圧下に維持してニッケルやコバルトを硫酸溶液中に浸出した浸出液を得、次いでこの浸出液に中和剤を添加するなどしてｐＨを調整して鉄やアルミなどの不純物を沈殿させて除去し、次いで不純物を除去した後の溶液に硫化水素ガスなどの硫化剤を添加し、ニッケルやコバルトを混合硫化物として沈殿させ、回収する方法がある。 One method for recovering nickel and cobalt from oxide ores containing nickel and cobalt is to maintain the oxide ore together with a sulfuric acid solution at high temperatures and pressures exceeding 200°C to obtain a leachate in which nickel and cobalt are leached into the sulfuric acid solution, and then a neutralizing agent is added to the leachate to adjust the pH and precipitate and remove impurities such as iron and aluminum. A sulfurizing agent such as hydrogen sulfide gas is then added to the solution after the impurities have been removed, and the nickel and cobalt are precipitated as mixed sulfides and recovered.
さらに前記方法によって得た混合硫化物は、塩素ガスなどを用いてニッケルやコバルトを浸出して塩化物溶液とし、この塩化物溶液をセメンテーション（置換）反応や中和反応などの方法に付して塩化物溶液中に残存する銅・鉄・ヒ素・亜鉛などの不純物の多くを除去し、さらに溶媒抽出などの方法を用いてニッケルとコバルトを分離し、それぞれを硫酸塩や塩化物などの化合物塩の形で回収したり、電解採取に付して高純度な電気ニッケルや電気コバルトとして回収することも行われている。 The mixed sulfide obtained by the above method is further leached with chlorine gas or the like to extract nickel and cobalt, forming a chloride solution, which is then subjected to a cementation (substitution) reaction or neutralization reaction to remove many of the impurities remaining in the chloride solution, such as copper, iron, arsenic, and zinc. The nickel and cobalt are then separated using a method such as solvent extraction, and each is recovered in the form of a compound salt, such as sulfate or chloride, or is subjected to electrowinning to recover high-purity electrolytic nickel or electrolytic cobalt.
上述するような方法を用いた場合、溶媒抽出で用いる抽出剤や抽出剤を希釈するために添加される希釈剤（以下まとめて「有機溶媒」という）には、金属イオンを含有する不純物（以下単に「金属不純物」という）が残存することがある。 When the above-mentioned methods are used, impurities containing metal ions (hereinafter simply referred to as "metal impurities") may remain in the extractant used in the solvent extraction and in the diluent added to dilute the extractant (hereinafter collectively referred to as "organic solvent").
残存する大きな原因は、一般に上述の塩化物溶液に含有される不純物の量が元々多く、セメンテーションや中和等の処理を１回程度実施しただけで完全に除去するのは困難なためである。 The main reason they remain is that the above-mentioned chloride solutions generally contain a large amount of impurities to begin with, and it is difficult to completely remove them by carrying out a single process such as cementation or neutralization.
具体的にはニッケル酸化鉱石の処理に用いた抽出始液には、回収対象のニッケルやコバルト以外にも亜鉛のような不純物が多量に含まれることがある。この亜鉛を完全に除去しようとして、中和等の処理をより厳格に行うと、ニッケルやコバルトが亜鉛などの金属不純物と共沈するなどしてロスとなるので、不純物除去方法としては採用し難い。 Specifically, the starting extraction liquid used to process nickel oxide ore can contain large amounts of impurities such as zinc in addition to the nickel and cobalt to be recovered. If more rigorous neutralization or other treatments are carried out in an attempt to completely remove this zinc, nickel and cobalt will co-precipitate with metal impurities such as zinc, resulting in losses, making this a difficult method to adopt for removing impurities.
そこで、これら有機溶媒中に含有される金属不純物を除去するための別の方法として、例えば、特許文献１～３の従来技術が提案されている。これらの従来技術は、逆抽出後の有機溶媒を中和工程に付すことで金属不純物を除去するものである。 As an alternative method for removing metal impurities contained in these organic solvents, the conventional techniques described in Patent Documents 1 to 3, for example, have been proposed. These conventional techniques remove metal impurities by subjecting the organic solvent after back extraction to a neutralization process.
特許文献１には、有機溶媒と不純物とを効率よく分離できる有機溶媒中の不純物除去方法が開示されている。具体的には、亜鉛などの不純物を含む有機溶媒に中和剤を添加して、中和澱物を生成する中和工程（一般的な亜鉛存在量の多さから「脱亜鉛工程」とも称する）と、中和澱物を含む有機溶媒を、中和澱物を含む水相と有機相とに油水分離する油水分離工程とを備え、中和工程において、有機溶媒のｐＨを７．９５～９．１５に調整するものである。中和工程では、中和澱物の粒径が大きくなることで中和澱物が水相に沈降する速度が速くなり、その結果分相性を高めることができて有機溶媒と不純物とを効率よく分離することができる。 Patent Document 1 discloses a method for removing impurities from an organic solvent, which can efficiently separate the organic solvent from the impurities. Specifically, the method includes a neutralization step (also called a "dezincing step" due to the generally high amount of zinc present) in which a neutralizing agent is added to an organic solvent containing impurities such as zinc to produce a neutralized precipitate, and an oil-water separation step in which the organic solvent containing the neutralized precipitate is separated into an aqueous phase containing the neutralized precipitate and an organic phase, and the pH of the organic solvent is adjusted to 7.95 to 9.15 in the neutralization step. In the neutralization step, the particle size of the neutralized precipitate increases, which increases the rate at which the neutralized precipitate settles into the aqueous phase, and as a result, phase separation can be improved and the organic solvent can be efficiently separated from the impurities.
特許文献２には、上記特許文献１の中和工程において、有機溶媒の温度を５０℃～６０℃に調整することで、有機溶媒の粘度を低下させ、中和澱物が水相に沈降する速度を速くし、分相性を高めることができて有機溶媒と不純物とを効率よく分離できる方法が開示されている。 Patent Document 2 discloses a method for efficiently separating the organic solvent from impurities by adjusting the temperature of the organic solvent to 50°C to 60°C in the neutralization step of Patent Document 1, thereby decreasing the viscosity of the organic solvent, accelerating the rate at which the neutralized precipitate settles into the aqueous phase, and increasing phase separation.
特許文献３には、上記特許文献１および特許文献２の中和工程において、有機溶媒に水を添加し有機溶媒を希釈することで粘度を低下させ、中和澱物が水相に沈降する速度が速くすることで、有機溶媒と不純物とを効率よく分離できる方法が開示されている。 Patent Document 3 discloses a method for efficiently separating the organic solvent from impurities in the neutralization process described in Patent Documents 1 and 2 above, in which water is added to the organic solvent to dilute the organic solvent, thereby decreasing the viscosity and increasing the rate at which the neutralized precipitate settles into the aqueous phase.
上記特許文献１～３の方法では、中和工程で有機溶媒に水酸化ナトリウム等の中和剤を添加して有機溶媒のアミンに付加した酸を脱離（不活性化）させ、同時に金属不純物を金属水酸化物の形態の中和澱物とする。次いで、この中和澱物を含んだ有機溶媒をデカンター等の油水分離装置を用いて中和澱物を含む水相（以下「重液」とも称する）と中和澱物が含まれない有機相（以下「軽液」とも称する）とに分離している。 In the methods of Patent Documents 1 to 3, a neutralizing agent such as sodium hydroxide is added to the organic solvent in the neutralization step to desorb (inactivate) the acid added to the amine in the organic solvent, and at the same time, metal impurities are converted into a neutralized precipitate in the form of metal hydroxide. Next, the organic solvent containing the neutralized precipitate is separated into an aqueous phase containing the neutralized precipitate (hereinafter also referred to as "heavy liquid") and an organic phase not containing the neutralized precipitate (hereinafter also referred to as "light liquid") using an oil-water separator such as a decanter.
上記の軽液は、金属不純物が除去された有機溶媒として酸性水溶液を添加されて再度活性化され、溶媒抽出工程での抽出段に繰り返されて溶媒抽出に再利用される。 The light liquid is reactivated by adding an acidic aqueous solution to the organic solvent from which metal impurities have been removed, and is reused in the extraction stage of the solvent extraction process.
一方、重液には少量の有機溶媒も混入することは避けらないので、有機溶媒は澱物溶解工程に送り塩酸を添加して溶解され、亜鉛などの金属不純物を含有する澱物溶解液と有機相を主とする澱物溶解後有機とに油水分離される。 On the other hand, since it is inevitable that a small amount of organic solvent will be mixed into the heavy liquid, the organic solvent is sent to the sediment dissolution process, where it is dissolved by adding hydrochloric acid, and the oil-water separation is performed into a sediment solution containing metal impurities such as zinc and a post-sediment dissolution organic phase consisting mainly of an organic phase.
澱物溶解液は金属不純物の水溶液なので、排水処理工程に送られ公知の方法で処理される。 Since the sediment solution is an aqueous solution of metal impurities, it is sent to a wastewater treatment process and treated using known methods.
一方、澱物溶解後有機は中和工程に繰り返されて、逆抽後有機に巻き込まれた水相や固形分を分離しやすくするための希釈剤として使用され、最終的には上述の軽液として溶媒抽出工程に繰り返されて有機溶媒として再利用される。 On the other hand, the organic solvent after dissolving the sediment is recycled to the neutralization process and used as a diluent to make it easier to separate the aqueous phase and solids that are caught up in the organic solvent after back extraction, and is finally recycled to the solvent extraction process as the light liquid mentioned above and reused as an organic solvent.
しかしながら、逆抽出後の有機溶媒には、上述の金属不純物の他にも、抽出剤や希釈剤の製造時から含まれていたり、使用に伴って有機溶媒が劣化して生成した有機系不純物も含有される。具体的な有機系不純物としては、例えばカルボン酸、スルホン酸等がある。
これらの有機系不純物は、有機溶媒の繰り返し使用に伴って次第に増加し蓄積し、ひいては有機溶媒による不純物の分離能力を低下させる問題がある。
However, in addition to the above-mentioned metal impurities, the organic solvent after stripping also contains organic impurities that were present in the extractant or diluent during production or that were generated by the deterioration of the organic solvent during use. Specific examples of organic impurities include carboxylic acids and sulfonic acids.
These organic impurities gradually increase and accumulate with repeated use of the organic solvent, which in turn reduces the ability of the organic solvent to separate impurities.
これら有機系不純物や金属系不純物の一つである鉄や亜鉛は、塩素イオン（塩化物イオン）との錯体（クロロ錯体）を形成して存在するが、とくに鉄や亜鉛のクロロ錯体は有機溶媒との結合が強く安定となる特徴があり、有機溶媒との分離は容易ではなかった。 Iron and zinc, which are among the organic and metallic impurities, exist by forming complexes (chloro complexes) with chlorine ions (chloride ions). However, the chloro complexes of iron and zinc in particular have the characteristic of being strongly and stably bound to organic solvents, making them difficult to separate from the organic solvent.
有機溶媒の分離能力が低下すると、品質や生産性の低下をもたらすことになるので有機溶媒を再生することが望まれる。しかしながら、工業的に効率な方法は見当たらず、解決すべき課題となっていた。 When the separation ability of the organic solvent decreases, it leads to a decrease in quality and productivity, so it is desirable to regenerate the organic solvent. However, there is no industrially efficient method available, and this has been an issue that needs to be resolved.
本発明は、不純物を含む有機溶媒から有機系不純物を除去する除去方法を提供することを目的とする。 The present invention aims to provide a method for removing organic impurities from an organic solvent containing impurities.
第１発明の有機溶媒中の有機系不純物の除去方法は、不純物を含む有機溶媒から有機系不純物を除去する方法であって、下記（１）～（４）を含む基本工程が、（１）不純物を含む有機溶媒に、硫酸を添加して、硫酸洗浄後液と硫酸洗浄後有機を得る硫酸洗浄工程、（２）前記硫酸洗浄後有機に中和剤を添加してｐＨを調整し、中和澱物と水相と有機相を有する洗浄後重液と有機相を含む洗浄後軽液に分離するアルカリ洗浄工程、（３）前記洗浄後重液に、硫酸を添加し、澱物溶解後有機と澱物溶解液を得る澱物溶解工程からなり、（４）前記澱物溶解後有機を前記アルカリ洗浄工程に繰り返すものであり、（５）上記アルカリ洗浄工程の前に劣化評価工程を実行し、劣化程度が許容できると評価された前記澱物溶解後有機を前記アルカリ洗浄工程に付すことを特徴とする。
第２発明の有機溶媒中の有機系不純物の除去方法は、第１発明において、前記基本工程に付す不純物を含む有機溶媒が、ニッケル、コバルト、亜鉛を含有する原料から溶媒抽出工程によりニッケルを含む抽出後液を分離して抽出後有機を得、前記抽出後有機を逆抽出工程でコバルトを含む逆抽出後液を分離して得た逆抽後有機であることを特徴とする。
第３発明の有機溶媒中の有機系不純物の除去方法は、第２発明において、前記基本工程に付す不純物を含む有機溶媒が、ニッケルとコバルトと亜鉛を含有する原料を酸または塩素ガスで浸出する浸出工程で抽出始液を得、次いで前記溶媒抽出工程と前記逆抽出工程を順に実行して得た逆抽後有機であることを特徴とする。
第４発明の有機溶媒中の有機系不純物の除去方法は、第２発明において、前記基本工程に付す不純物を含む有機溶媒が、前記逆抽出後有機に中和剤を添加し亜鉛を分離する亜鉛分離工程で、分離後重液と分離後軽液を得、前記分離後重液に塩酸を添加して分離後澱物溶解液を分離する澱液分離工程で得た分離後澱物溶解後有機であることを特徴とする。
第５発明の有機溶媒中の有機系不純物の除去方法は、第１発明において、前記アルカリ洗浄工程において、硫酸洗浄後有機と中和剤を混合した際のｐＨを６以上１２以下の範囲に維持することを特徴とする。
第６発明の有機溶媒中の有機系不純物の除去方法は、第５発明において、前記中和剤が、中和剤を含む溶液もしくはスラリーの形態で添加されることを特徴とする。
第７発明の有機溶媒中の有機系不純物の除去方法は、第１発明において、前記不純物を含む有機溶媒を前記基本工程に付す前に、粘性を調整する粘性調整工程に付すことを特徴とする。
第８発明の有機溶媒中の有機系不純物の除去方法は、第１発明において、前記劣化評価工程における劣化評価の判断基準が、前記澱物溶解後有機の粘度を１６０ｍＰａ・ｓ未満とすることを特徴とする。
The method for removing organic impurities in an organic solvent according to the first invention is a method for removing organic impurities from an organic solvent containing impurities, and is characterized in that it comprises the following basic steps (1) to (4): (1) a sulfuric acid washing step of adding sulfuric acid to an organic solvent containing impurities to obtain a sulfuric acid washing liquid and a sulfuric acid washing organic, (2) an alkali washing step of adding a neutralizing agent to the sulfuric acid washing organic to adjust the pH and separate the sulfuric acid washing organic into a post-washing heavy liquid having a neutralized precipitate, an aqueous phase, and an organic phase, and a post-washing light liquid containing an organic phase, (3) a sediment dissolving step of adding sulfuric acid to the post-washing heavy liquid to obtain a sediment dissolved organic and a sediment dissolved liquid, (4) the sediment dissolved organic is subjected to the alkali washing step again, and (5) a deterioration evaluation step is carried out before the alkali washing step, and the sediment dissolved organic evaluated to have an acceptable degree of deterioration is subjected to the alkali washing step.
The method for removing organic impurities in an organic solvent of the second invention is characterized in that in the first invention, the impurity-containing organic solvent to be subjected to the basic steps is a strip-extracted organic solvent obtained by separating a post-extraction liquid containing nickel from a raw material containing nickel, cobalt, and zinc in a solvent extraction step to obtain a post-extraction organic solvent, and separating a strip-extraction liquid containing cobalt from the post-extraction organic solvent in a strip-extraction step.
The method for removing organic impurities from an organic solvent of the third invention is characterized in that, in the second invention, the impurity-containing organic solvent to be subjected to the basic steps is a back-extracted organic solvent obtained by obtaining an extraction starting solution in a leaching step in which a raw material containing nickel, cobalt, and zinc is leached with an acid or chlorine gas, and then carrying out the solvent extraction step and the back extraction step in that order.
The method for removing organic impurities in an organic solvent according to the fourth invention is characterized in that, in the second invention, the impurity-containing organic solvent to be subjected to the basic steps is a separated sediment-dissolved organic solvent obtained in a starch separation step in which a neutralizing agent is added to the post-stripping organic solvent to separate zinc, a separated heavy liquid and a separated light liquid are obtained, and hydrochloric acid is added to the separated heavy liquid to separate a separated sediment-dissolved liquid.
The method for removing organic impurities from an organic solvent of the fifth invention is characterized in that in the first invention, in the alkali washing step, the pH when the organic solvent and the neutralizing agent are mixed after the sulfuric acid washing is maintained in the range of 6 or more and 12 or less.
The method for removing organic impurities in an organic solvent according to a sixth aspect of the present invention is characterized in that, in the fifth aspect of the present invention, the neutralizing agent is added in the form of a solution or slurry containing the neutralizing agent.
The method for removing organic impurities from an organic solvent of the seventh invention is characterized in that, in the first invention, the organic solvent containing the impurities is subjected to a viscosity adjustment step of adjusting the viscosity before being subjected to the basic step.
The method for removing organic impurities from an organic solvent of the eighth invention is characterized in that, in the first invention, the criterion for judging deterioration evaluation in the deterioration evaluation step is that the viscosity of the organic solvent after dissolution of the sediment is less than 160 mPa·s.
第１発明によれば、硫酸洗浄工程で金属系不純物を除去したのち、有機系不純物を含む硫酸洗浄後有機をアルカリ洗浄工程に付すと不純物が除去された洗浄後軽液と不純物が残留している洗浄後重液が得られる。洗浄後重液は澱物溶解工程で澱物溶解液と澱物溶解後有機に分離され、澱物溶解後有機は劣化評価工程で劣化が許容されると評価されたものがアルカリ洗浄工程に繰り返される。このため、不純物が充分に除去された洗浄後軽液が得られ、再び有機溶媒として利用できるようになる。
第２発明によれば、ニッケルコバルト製錬工程で生ずる逆抽出後有機を不純物の少ない有機溶媒に再生できる。
第３発明によれば、浸出工程で抽出始液を得ると、この抽出始液は液として扱えるので後工程である溶媒抽出工程と逆抽出工程が実行しやすくなる。
第４発明によれば、亜鉛分離工程で亜鉛を分離した後の分離後重液について澱液分離工程に付すと分離後澱物溶解後有機が得られ、基本工程での不純物除去に適した有機溶媒が得られる。
第５発明によれば、ｐＨが適正な範囲なので、テトラクロロベンゼンスルホン酸、ヘプタン酸、トリクロロメタンスルホン酸を除去できる。
第６発明によれば、中和剤が溶液もしくはスラリーであることでｐＨの測定が容易に行えるので、アルカリ洗浄工程中のｐＨ管理が適正に行える。
第７発明によれば、粘度調整工程において有機溶媒を低粘性に調整しておくと、基本工程における不純物除去が効率良く行える。
第８発明によれば、劣化基準基準を有機の粘度１６０ｍＰａ・ｓ未満とし、基準値以上の有機を系外に払い出すことで、濃縮した有機劣化物を除去できる。このため、澱物溶解工程の溶解反応が効率良く行える。
According to the first invention, after removing metal-based impurities in the sulfuric acid washing step, the sulfuric acid-washed organics containing organic impurities are subjected to an alkali washing step to obtain a light washing liquid from which the impurities have been removed and a heavy washing liquid from which the impurities remain. The heavy washing liquid is separated into a sediment-dissolving liquid and a sediment-dissolving organic in the sediment dissolving step, and the sediment-dissolving organics that are evaluated as having acceptable deterioration in the deterioration evaluation step are repeated in the alkali washing step. As a result, a light washing liquid from which the impurities have been sufficiently removed is obtained, and can be reused as an organic solvent.
According to the second invention, the organic solvent after stripping generated in the nickel-cobalt smelting process can be regenerated into an organic solvent with few impurities.
According to the third invention, when an extraction starting liquid is obtained in the leaching step, this extraction starting liquid can be handled as a liquid, making it easier to carry out the subsequent solvent extraction step and stripping step.
According to the fourth invention, when the heavy liquid obtained after the zinc is separated in the zinc separation step is subjected to the starch separation step, an organic solvent is obtained after the separation starch is dissolved, and an organic solvent suitable for removing impurities in the basic step is obtained.
According to the fifth invention, since the pH is within an appropriate range, tetrachlorobenzenesulfonic acid, heptanoic acid, and trichloromethanesulfonic acid can be removed.
According to the sixth aspect of the present invention, since the neutralizing agent is in the form of a solution or a slurry, the pH can be easily measured, and therefore the pH can be appropriately controlled during the alkaline washing step.
According to the seventh aspect of the present invention, if the viscosity of the organic solvent is adjusted to a low level in the viscosity adjusting step, impurities can be removed efficiently in the basic step.
According to the eighth aspect of the present invention, the deterioration standard is set to a viscosity of less than 160 mPa·s, and organic matter having a viscosity equal to or greater than the standard value is discharged from the system, thereby making it possible to remove concentrated organic deteriorated matter. This makes it possible to efficiently carry out the dissolution reaction in the sediment dissolution step.
本発明に係る有機系不純物除去方法を、図１および図４に基づき説明する。
図１に示す本発明の基本工程は、不純物を含む有機溶媒から有機系不純物を除去する方法であって、
（１）不純物を含む有機溶媒に、硫酸を添加して、硫酸洗浄後液と硫酸洗浄後有機を得る硫酸洗浄工程Ｓ１、
（２）前記硫酸洗浄後有機に中和剤を添加してｐＨを調整し、中和澱物と水相と有機相を有する洗浄後重液と有機相を含む洗浄後軽液に分離するアルカリ洗浄工程Ｓ２、
（３）前記洗浄後重液に、硫酸を添加し、澱物溶解後有機と澱物溶解液を得る澱物溶解工程Ｓ３からなり、
（４）前記澱物溶解後有機を前記アルカリ洗浄工程Ｓ２に繰り返すものである。
本発明では、さらに図４に示すように、（５）上記アルカリ洗浄工程の前に劣化評価工程を実行し、劣化程度が許容できると評価された前記澱物溶解後有機を前記アルカリ洗浄工程に付すことを特徴とする。
The method for removing organic impurities according to the present invention will be described with reference to FIGS.
The basic steps of the present invention shown in FIG. 1 are a method for removing organic impurities from an organic solvent containing impurities,
(1) A sulfuric acid washing step S1 in which sulfuric acid is added to an organic solvent containing impurities to obtain a sulfuric acid washed solution and a sulfuric acid washed organic;
(2) an alkali washing step S2 in which a neutralizing agent is added to the organic phase after the sulfuric acid washing to adjust the pH and separate the organic phase into a post-wash heavy liquid having a neutralized precipitate, an aqueous phase, and an organic phase, and a post-wash light liquid having an organic phase;
(3) A sediment dissolving step S3 in which sulfuric acid is added to the post-wash heavy liquid to obtain a sediment dissolving solution and an organic solvent after dissolving the sediment;
(4) After dissolving the sediment, the organic layer is subjected to the alkaline washing step S2 again.
The present invention is further characterized in that, as shown in FIG. 4, (5) a deterioration evaluation step is carried out before the alkaline washing step, and the organic matter after dissolving sediment, the deterioration of which is evaluated to be acceptable, is subjected to the alkaline washing step.
上記除去方法によれば、硫酸洗浄工程Ｓ１で金属系不純物を硫酸洗浄後液に含ませて除去するので、硫酸洗浄後有機には有機系不純物が含まれることになる。この硫酸洗浄後有機はアルカリ洗浄工程Ｓ２で、不純物が除去された洗浄後軽液（有機溶媒）と不純物が残留している洗浄後重液に分離される。洗浄後重液は澱物溶解工程Ｓ３で澱物溶解液と澱物溶解後有機に分離され、澱物溶解後有機は再びアルカリ洗浄工程Ｓ２に繰り返されて、アルカリ洗浄される。上記のアルカリ洗浄工程Ｓ２で繰り返し洗浄された洗浄後軽液は有機系不純物が充分に除去されているので、再利用可能な有機溶媒となる。なお、劣化評価工程Ｓ２２については後述する。 According to the above removal method, the metal-based impurities are removed by being contained in the sulfuric acid washing liquid in the sulfuric acid washing step S1, so the sulfuric acid washing organic contains organic impurities. This sulfuric acid washing organic is separated in the alkaline washing step S2 into a post-washing light liquid (organic solvent) from which the impurities have been removed and a post-washing heavy liquid from which the impurities remain. The post-washing heavy liquid is separated into a sediment dissolving liquid and a post-sediment dissolving organic in the sediment dissolving step S3, and the post-sediment dissolving organic is again repeated in the alkaline washing step S2 for alkaline washing. The post-washing light liquid that has been repeatedly washed in the alkaline washing step S2 has had organic impurities sufficiently removed from it, so it becomes a reusable organic solvent. The deterioration evaluation step S22 will be described later.
本発明により有機系不純物を除去する対象には、「不純物を含む有機溶媒」であれば、とくに制限はない。ただし、ニッケルコバルト製錬工程における溶媒抽出で用いる抽出剤（有機溶媒）に蓄積した不純物や抽出剤自身が劣化した有機系不純物を除去する場合に好適に利用できる。 The subject from which organic impurities can be removed by the present invention is not particularly limited, so long as it is an "organic solvent containing impurities." However, the present invention can be suitably used to remove impurities that have accumulated in the extractant (organic solvent) used in solvent extraction in the nickel-cobalt smelting process, or organic impurities that have deteriorated in the extractant itself.
本発明により不純物が除去された有機溶媒は再生された有機溶媒として、再び溶媒抽出に用いる抽出剤やその他の用途に再利用できる。 The organic solvent from which impurities have been removed by the present invention can be reused as an extractant for solvent extraction or for other purposes as a regenerated organic solvent.
図２に基づきニッケルコバルト製錬工程の概略を説明する。
ニッケル、コバルト、亜鉛を含有する原料から溶媒抽出工程Ｓ１２により抽出後液と抽出後有機を得る。抽出後液からは必要な工程を経てニッケル製品を得る。抽出後有機は逆抽出工程Ｓ１３に付する。逆抽出工程Ｓ１３では逆抽出後液とコバルトとニッケル以外の不純物を含む逆抽出後有機を得る。逆抽出後液からは必要な工程を経てコバルト製品を得ることができるが、逆抽出後有機は金属系および有機系の不純物が蓄積したものとなっている。この不純物を除去すると、有機溶媒として再生できるので、本発明の基本工程に付す意義がある。
The nickel-cobalt smelting process will be outlined with reference to FIG.
A post-extraction liquid and a post-extraction organic are obtained from a raw material containing nickel, cobalt, and zinc by a solvent extraction step S12. A nickel product is obtained from the post-extraction liquid through necessary steps. The post-extraction organic is subjected to a stripping step S13. In the stripping step S13, a post-extraction liquid and a post-stripping organic containing impurities other than cobalt and nickel are obtained. A cobalt product can be obtained from the post-stripping liquid through necessary steps, but the post-stripping organic contains accumulated metallic and organic impurities. If these impurities are removed, it can be regenerated as an organic solvent, and therefore it is meaningful to subject it to the basic steps of the present invention.
図２に示す製錬工程では、前記溶媒抽出工程Ｓ１２の前に浸出工程Ｓ１１をおくことが好ましい場合がある。ニッケルとコバルトと亜鉛を含有する原料を酸または塩素ガスで浸出する浸出工程Ｓ１１を実行すると、ニッケルとコバルトを含有する抽出始液が得られる。この抽出始液は液体として扱えるので、後工程である溶媒抽出工程Ｓ１２と逆抽出工程Ｓ１３が実行しやすくなる。 In the smelting process shown in FIG. 2, it may be preferable to perform a leaching process S11 before the solvent extraction process S12. When the leaching process S11 is performed, in which a raw material containing nickel, cobalt, and zinc is leached with an acid or chlorine gas, an extraction liquid containing nickel and cobalt is obtained. Since this extraction liquid can be handled as a liquid, it becomes easier to perform the subsequent processes of the solvent extraction process S12 and the back extraction process S13.
上記のようにニッケルコバルト製錬工程で得られた逆抽出後有機には、亜鉛などの金属系不純物のほか有機系不純物が残留している。金属系不純物が少量の場合は、逆抽出後有機を不純物除去工程の基本工程（図１）に直接付してもよい。しかし、金属系不純物が多い場合は、予め金属系不純物を除去する方が除去効率が高くなるため、図３に示す後処理工程に付したうえで逆抽出後有機を、有機系不純物を除去する基本工程に供するのが好ましい。 As described above, the post-stripping organic matter obtained in the nickel-cobalt smelting process contains organic impurities as well as metal impurities such as zinc. When the amount of metal impurities is small, the post-stripping organic matter may be directly subjected to the basic process of the impurity removal process (Figure 1). However, when the amount of metal impurities is large, it is more efficient to remove the metal impurities in advance, so it is preferable to subject the post-stripping organic matter to the post-treatment process shown in Figure 3 and then to the basic process of removing organic impurities.
図３に示す後処理工程を説明する。
ニッケルコバルト製錬工程で得た逆抽出後有機は亜鉛分離工程Ｓ１４に付され、水酸化ナトリウムなどの中和剤を添加しｐＨを８～９に調整して分離後重液と分離後軽液に分離する。有機物を主とする分離後軽液は塩酸等を添加して活性化させて再び有機溶媒として利用できる。たとえば、得られた分離後軽液は図２に点線で示すように溶媒抽出工程Ｓ１２へ溶媒として供される。一方、分離後重液は澱物と一部の有機物を含んでいるので澱液分離工程Ｓ１５に付し、塩酸を添加して亜鉛などの金属系不純物を含む分離後澱物溶解液と分離後澱物溶解後有機に分離する。このようにして得られた分離後澱物溶解後有機には有機系不純物と一部の再抽出された亜鉛等の金属不純物も含んだ有機となっている。この分離後澱物溶解後有機が図１の基本工程に供される。
The post-treatment process shown in FIG. 3 will now be described.
The organic matter after stripping obtained in the nickel-cobalt smelting process is subjected to a zinc separation process S14, where a neutralizing agent such as sodium hydroxide is added to adjust the pH to 8-9, and the organic matter after separation is separated into a heavy liquid after separation and a light liquid after separation. The light liquid after separation, which is mainly composed of organic matter, can be activated by adding hydrochloric acid or the like and reused as an organic solvent. For example, the light liquid after separation is supplied as a solvent to a solvent extraction process S12 as shown by the dotted line in FIG. 2. On the other hand, the heavy liquid after separation contains sediment and some organic matter, so it is supplied to a sediment separation process S15, where hydrochloric acid is added to separate it into a separated sediment solution containing metal impurities such as zinc and a separated sediment solution after separation. The separated sediment solution organic matter obtained in this way contains organic impurities and some re-extracted metal impurities such as zinc. This separated sediment solution organic matter is supplied to the basic process in FIG. 1.
上記の後処理工程で得た分離後澱物溶解後有機に含まれる有機系不純物には、カルボン酸が劣化し分解したヘプタン酸や、スルホン酸が劣化して生じたトリクロロメタンスルホン酸やテトラクロロベンゼンスルホン酸に代表される有機系不純物がある。 The organic impurities contained in the organic residue after separation and dissolution of the sediment obtained in the above post-treatment process include organic impurities such as heptanoic acid, which is formed when carboxylic acids are degraded and decomposed, and trichloromethanesulfonic acid and tetrachlorobenzenesulfonic acid, which are formed when sulfonic acids are degraded.
上述するヘプタン酸などの有機系不純物は、酸の添加によりｐＨが低下すると有機相へ移動してしまうので、有機溶媒が有機系不純物が含まれたまま繰り返されると、有機系不純物を払い出すことができず蓄積してしまう。 Organic impurities such as the above-mentioned heptanoic acid move to the organic phase when the pH is lowered by adding an acid, so if the organic solvent is repeatedly used while still containing organic impurities, the organic impurities cannot be expelled and accumulate.
しかるに、本発明の不純物除去方法（図１の基本工程）を用いると、後述するように上記有機系不純物をほとんど除去して再び有機溶媒として利用することができる。 However, by using the impurity removal method of the present invention (basic steps in Figure 1), most of the organic impurities can be removed and the organic solvent can be reused, as described below.
上記に概要を説明した不純物除去方法の実施形態を、以下に図１を参酌しながら詳細に説明する。
（１）硫酸洗浄工程Ｓ１
不純物を含む有機溶媒、たとえば、図３に示す処理で得た分離後澱物溶解後有機を硫酸洗浄工程Ｓ１に付す。硫酸洗浄工程Ｓ１では、不純物を含む有機溶媒に硫酸を添加し、硫酸洗浄後液と硫酸洗浄後有機とを得る。
The embodiment of the impurity removal method outlined above will be described in detail below with reference to FIG.
(1) Sulfuric acid washing step S1
An organic solvent containing impurities, for example, an organic solvent after dissolving separated sediment obtained in the process shown in Fig. 3, is subjected to a sulfuric acid washing step S1. In the sulfuric acid washing step S1, sulfuric acid is added to an organic solvent containing impurities to obtain a sulfuric acid washed solution and a sulfuric acid washed organic.
不純物を含む有機溶媒を硫酸洗浄すると、主に鉄と塩素との錯体を分離し、それによって固形物などの生成原因となる鉄を除去できる。
この理由は硫酸を添加することで、分離後澱物溶解後有機中の塩化物濃度が薄まり、鉄と亜鉛と銅が塩化物溶液中で形成するクロロ錯イオン(ＦｅＣｌ４
－）を壊すことができ、その結果有機溶媒から除去されやすくなるためである。
When an organic solvent containing impurities is washed with sulfuric acid, the complexes between iron and chlorine are separated, and the iron that causes the formation of solids and the like can be removed.
The reason for this is that by adding sulfuric acid, the chloride concentration in the organic solution is diluted after separation and dissolution of the sediment, and the chloro complex ion (FeCl 4 - ) formed by iron, zinc, and copper in the chloride solution is destroyed, making it easier to remove from the organic solvent.
この結果、鉄、亜鉛、銅などの金属が硫酸洗浄後液に含められて除去される。図５に示すように、混合する硫酸溶液酸濃度（横軸）は、０．１ｍｏｌ／Ｌ以上とすることで、鉄（Ｆｅ）、亜鉛（Ｚｎ）、銅（Ｃｕ）の洗浄効果が高まる。 As a result, metals such as iron, zinc, and copper are removed by being included in the post-sulfuric acid cleaning solution. As shown in Figure 5, by setting the acid concentration (horizontal axis) of the mixed sulfuric acid solution to 0.1 mol/L or more, the cleaning effect of iron (Fe), zinc (Zn), and copper (Cu) is improved.
硫酸洗浄工程Ｓ１で鉄、亜鉛、銅などの金属を除去しておけば、澱物生成が抑制されるので、後工程で溶液の固液分離（分相性）が向上し、有機系不純物を除去しやすくなる。この結果、アルカリ洗浄工程Ｓ２での洗浄後重液と洗浄後軽液の分離性が改善でき、さらなる後工程である澱物溶解工程Ｓ３での澱物溶解性も改善する。 If metals such as iron, zinc, and copper are removed in the sulfuric acid washing step S1, sediment formation is suppressed, improving the solid-liquid separation (phase separation) of the solution in the subsequent step, making it easier to remove organic impurities. As a result, the separation of the heavy liquid after washing and the light liquid after washing in the alkaline washing step S2 can be improved, and the solubility of the sediment in the further subsequent sediment dissolving step S3 is also improved.
この硫酸洗浄工程Ｓ１で除去されるのは金属系不純物なので、出発原料としての分離後澱物溶解後有機に金属系不純物が含有されないか許容値以下の場合は硫酸洗浄工程Ｓ１は理論上必須とはいえない。しかしながら、金属系不純物を安定して含有させないことは工業的には困難なので、この硫酸洗浄工程Ｓ１によって金属系の不純物を安定して除去し、また有機相と水相との分離性を向上するには事実上必須とされる。 Since metal impurities are removed in this sulfuric acid washing step S1, if the organic phase after separation and dissolution of the sediment does not contain metal impurities or the impurities are below the allowable value, the sulfuric acid washing step S1 is not theoretically necessary. However, since it is industrially difficult to ensure that metal impurities are not contained stably, this sulfuric acid washing step S1 is practically necessary to stably remove metal impurities and improve the separability between the organic phase and the aqueous phase.
また、分離後澱物溶解後有機に含有される金属系不純物が許容値以下の場合は分離後澱物溶解後有機の全量を硫酸洗浄工程Ｓ１に付す必要はなく、直ちにアルカリ洗浄工程Ｓ２に付してもよい。 In addition, if the metal impurities contained in the organic solution after separation and dissolution of the sediment are below the allowable value, it is not necessary to subject the entire organic solution after separation and dissolution of the sediment to the sulfuric acid washing step S1, and it may be immediately subjected to the alkaline washing step S2.
（２）アルカリ洗浄工程Ｓ２
硫酸洗浄工程Ｓ１によって得た硫酸洗浄後有機は、中和剤を添加してｐＨを調整するアルカリ洗浄工程Ｓ２に付される。中和剤によってｐＨを上げることで、有機系不純物を水相へと移行させ、次いで有機と水相を分離すると、有機系不純物が除去された洗浄後軽液と洗浄後重液とに分離される。洗浄後軽液は不純物が除去された有機溶媒として再利用でき、洗浄後重液は有機系不純物を含んでいるので、次の澱物溶解工程Ｓ３に付される。
(2) Alkaline cleaning step S2
The sulfuric acid washed organic phase obtained in the sulfuric acid washing step S1 is subjected to an alkali washing step S2 in which a neutralizing agent is added to adjust the pH. By increasing the pH with the neutralizing agent, organic impurities are transferred to the aqueous phase, and the organic and aqueous phases are then separated into a post-wash light liquid from which the organic impurities have been removed and a post-wash heavy liquid. The post-wash light liquid can be reused as an organic solvent from which impurities have been removed, and the post-wash heavy liquid contains organic impurities and is therefore subjected to the next sediment dissolving step S3.
アルカリ洗浄工程Ｓ２におけるｐＨ調整は、中和剤を添加してｐＨを６以上１２以下、好ましくはｐＨを８以上１２以下、より好ましくはｐＨ９以上１２以下、の範囲に維持するとよい。 In the alkaline washing step S2, the pH is adjusted by adding a neutralizing agent to maintain the pH in the range of 6 to 12, preferably 8 to 12, and more preferably 9 to 12.
ｐＨが６未満であると有機系不純物をほとんど除去できない。ｐＨが６以上になるとテトラクロロベンゼンスルホン酸を除去でき、さらにｐＨが８以上ではヘプタン酸もほぼ完全に除去できる。さらにｐＨが９以上ではトリクロロメタンスルホン酸もほぼ完全に除去できる。 If the pH is less than 6, organic impurities are hardly removed. If the pH is 6 or higher, tetrachlorobenzenesulfonic acid can be removed, and if the pH is 8 or higher, heptanoic acid can be almost completely removed. Furthermore, if the pH is 9 or higher, trichloromethanesulfonic acid can be almost completely removed.
ｐＨが１２を超える強アルカリ域では、除去効果の向上はほとんど見られず、むしろコストや設備材料の耐久性や取り扱い面の安全性などの点でメリットはない。 In the strongly alkaline range with a pH above 12, there is little improvement in the removal effect, and there are no benefits in terms of cost, durability of equipment materials, or safety in handling.
上記のｐＨ範囲に調整することで、有機系不純物を洗浄後重液に分配させ、有機系不純物が除去された洗浄後軽液が得られる。 By adjusting the pH to the above range, organic impurities are distributed into the heavy liquid after cleaning, and a light liquid after cleaning from which the organic impurities have been removed is obtained.
アルカリ洗浄工程Ｓ２で得た洗浄後軽液は、不純物が除去されているが一部の水相や澱物も含有している。その洗浄後軽液の一部は図１の点線で示すように、アルカリ洗浄工程Ｓ２に付してもよい。金属系不純物と有機系不純物が分離された洗浄後軽液を繰り返すことで、硫酸洗浄後有機を希釈することと同じ効果が得られ、洗浄後重液と洗浄後軽液の分離性も向上する。 The light liquid after washing obtained in the alkaline washing step S2 has had impurities removed, but still contains some aqueous phase and sediment. A portion of the light liquid after washing may be subjected to the alkaline washing step S2, as shown by the dotted line in Figure 1. By repeating the light liquid after washing from which metallic impurities and organic impurities have been separated, the same effect as diluting the organic after sulfuric acid washing can be obtained, and the separation of the heavy liquid after washing and the light liquid after washing is also improved.
また、図３に点線で示すように、基本工程のアルカリ洗浄工程Ｓ２で得た洗浄後軽液の大部分を後処理工程を始めるときの亜鉛分離工程Ｓ１４に付す逆抽出後有機に供してもよい。この場合、逆抽出後有機を希釈する効果が得られ、亜鉛分離工程Ｓ１４や澱液分離工程Ｓ１５が進めやすくなる。 Also, as shown by the dotted line in Figure 3, most of the post-wash light liquid obtained in the basic alkaline washing process S2 may be used as the post-stripping organics to be subjected to the zinc separation process S14 when starting the post-treatment process. In this case, the effect of diluting the post-stripping organics is obtained, making it easier to proceed with the zinc separation process S14 and the sediment separation process S15.
図１に示すアルカリ洗浄工程Ｓ２においては、中和剤は溶液もしくはスラリーの形態で添加される。 In the alkaline washing step S2 shown in Figure 1, the neutralizing agent is added in the form of a solution or slurry.
中和剤としては、水酸化ナトリウムなどの溶液を用いることができる。水酸化ナトリウムの結晶など固体の中和剤も実際には有機相に巻き込まれた水相分があるので、使用できるが、溶媒が完全に有機溶媒のみであるとｐＨの測定ができないので現実的でない。 As a neutralizing agent, a solution such as sodium hydroxide can be used. Solid neutralizing agents such as sodium hydroxide crystals can also be used because they actually have an aqueous phase that is entrained in the organic phase, but if the solvent is entirely organic solvent, it is not practical because the pH cannot be measured.
アルカリ洗浄工程Ｓ２におけるアルカリ洗浄による有機系不純物の除去は、とくにカルボン酸に由来するナトリウム塩を形成する有機酸を不純物として含む有機溶媒に対して、効果的に機能する。 The removal of organic impurities by alkaline washing in the alkaline washing step S2 is particularly effective for organic solvents that contain, as impurities, organic acids that form sodium salts derived from carboxylic acids.
（３）澱物溶解工程Ｓ３
アルカリ洗浄工程Ｓ２で得られた洗浄後重液は、澱物溶解工程Ｓ３に供される。澱物溶解工程Ｓ３では、硫酸を用いて澱物溶解後有機と澱物溶解液とに分離される。ここで用いる硫酸には、新しい硫酸のほか硫酸洗浄工程Ｓ１で得た硫酸洗浄後液を用いてもよい。澱物溶解工程Ｓ３では硫酸を添加することで鉄のクロロ錯体の形成を抑制して、有機相に抽出されないようにしている。このため、澱物溶解後有機は鉄や銅、亜鉛をほとんど含まないものとなっている。
(3) Sediment dissolving step S3
The washed heavy liquid obtained in the alkali washing step S2 is supplied to the sediment dissolving step S3. In the sediment dissolving step S3, sulfuric acid is used to separate the sediment dissolved organic phase and the sediment dissolved liquid. The sulfuric acid used here may be fresh sulfuric acid or the sulfuric acid washed liquid obtained in the sulfuric acid washing step S1. In the sediment dissolving step S3, sulfuric acid is added to suppress the formation of iron chloro complexes, so that they are not extracted into the organic phase. As a result, the sediment dissolved organic phase contains almost no iron, copper, or zinc.
（４）繰り返し処理
得られた澱物溶解後有機は、アルカリ洗浄工程Ｓ２に繰り返され、必要な回数だけアルカリ洗浄される。
澱物溶解液は公知の処理方法を用いる排水処理工程で処理され、排水として系外に放出される。
(4) Repeated Treatment The obtained precipitate-dissolved organic layer is repeatedly subjected to the alkaline washing step S2 and washed with alkaline as many times as necessary.
The sediment-dissolved liquid is treated in a wastewater treatment process using a known treatment method, and is discharged outside the system as wastewater.
以上のように、図１に示す基本処理工程を実行すると、有機溶媒中に蓄積した不純物、とくに有機系不純物を充分に除去することができる。このようにして有機系不純物を分離した有機溶媒は、種々の用途に再利用することができる。とくに、本発明の除去方法では、有機系不純物としてナトリウム塩を形成する有機酸に対し効果がある。さらに有機酸の中でもカルボン酸に由来する場合に顕著な効果がある。 As described above, by carrying out the basic processing steps shown in Figure 1, impurities accumulated in the organic solvent, particularly organic impurities, can be sufficiently removed. The organic solvent from which the organic impurities have been separated in this manner can be reused for various purposes. In particular, the removal method of the present invention is effective against organic acids that form sodium salts as organic impurities. Furthermore, it is particularly effective when the organic acids are derived from carboxylic acids.
つぎに、図４に基づき、粘性調整工程Ｓ２１と劣化評価工程Ｓ２２を説明する。 Next, the viscosity adjustment process S21 and the deterioration evaluation process S22 will be explained based on FIG. 4.
（粘性調整工程Ｓ２１）
図３に示す澱液分離工程Ｓ１５で得られた分離後澱物溶解後有機が有機相と水相の分離性に問題が無い場合は、必須ではないが工業的な操業を行う場合は、分離後澱物溶解後有機の粘性を調整したうえで硫酸洗浄工程Ｓ１に付すことが好ましい。
(Viscosity adjusting step S21)
When the separated organic phase after dissolving the sediment obtained in the starch liquid separation step S15 shown in FIG. 3 has no problem in terms of separability into an organic phase and an aqueous phase, it is preferable, although not essential, to subject the separated organic phase after dissolving the sediment to the sulfuric acid washing step S1 after adjusting its viscosity in the case of industrial operation.
有機溶媒には、それまで既に金属系不純物の多くが分離されているが、なお多くの金属イオンが抽出され同時に有機劣化物も含まれる状態が多く、粘性が高くなっていることが多い。この場合、高粘性では有機溶媒への不純物を含んだ水相の巻き込みも増加し、不純物の除去が効率よく進まない。 Although many of the metal impurities have already been separated from the organic solvent, many metal ions are still extracted and organic degradation products are often still present, resulting in high viscosity. In this case, high viscosity also increases the entrainment of the aqueous phase containing impurities into the organic solvent, making the removal of impurities less efficient.
そこで、粘性調整工程Ｓ２１で逆抽出後有機や洗浄後有機を添加し、有機溶媒を低粘性に調整して不純物除去が効率良く行えるようにする。そのうえで、硫酸洗浄工程Ｓ１、アルカリ洗浄工程Ｓ２、澱物溶解工程Ｓ３からなる基本工程に付すとよい。 Therefore, in the viscosity adjustment process S21, the organic solvent after back extraction and the organic solvent after washing are added to adjust the viscosity of the organic solvent to low levels so that impurities can be removed efficiently. After that, it is recommended to carry out the basic processes consisting of the sulfuric acid washing process S1, the alkali washing process S2, and the sediment dissolving process S3.
（劣化評価工程Ｓ２２）
基本工程で得た澱物溶解後有機は劣化評価工程Ｓ２２に付すことが好ましい。有機溶媒の劣化程度を評価する方法としては、例えば粘度を測定する方法がある。粘度が一定粘度以下ならば、澱物溶解後有機はアルカリ洗浄工程Ｓ２に繰り返され、不純物の除去率が高くなった洗浄後軽液はコバルト抽出のための有機溶媒として再度利用される。
(Deterioration evaluation step S22)
The organic solvent after dissolving the sediment obtained in the basic process is preferably subjected to a deterioration evaluation process S22. The degree of deterioration of the organic solvent can be evaluated, for example, by measuring the viscosity. If the viscosity is below a certain level, the organic solvent after dissolving the sediment is returned to the alkaline washing process S2, and the light liquid after washing, which has a high impurity removal rate, is reused as an organic solvent for cobalt extraction.
澱物溶解後有機が、一定粘度以上ならば劣化しており再利用できないと評価できる。劣化した有機溶媒は、公知の廃有機処理に付し処分すればよい。 If the organic solvent has a certain viscosity or higher after dissolving the sediment, it can be evaluated as having deteriorated and not being able to be reused. The deteriorated organic solvent can be disposed of by known waste organic solvent treatment methods.
劣化評価工程Ｓ２２における劣化評価の判断基準は、澱物溶解後有機の粘度を１６０ｍＰａ・ｓ未満とするのが好ましい。澱物溶解後有機の粘度が基準値である１６０ｍＰａ・ｓ以上だと澱物の溶け残りが発生するが、基準値未満だと澱物の溶け残りが発生しないからである。
上記の基準値以上の有機は系外に払い出すことで、濃縮した有機劣化物を除去できる。このため、澱物溶解工程Ｓ３の溶解反応が効率良く行える。
The criterion for the deterioration evaluation in the deterioration evaluation step S22 is preferably a viscosity of the organic solution after dissolving the sediment of less than 160 mPa·s. If the viscosity of the organic solution after dissolving the sediment is equal to or higher than the reference value of 160 mPa·s, some sediment will remain undissolved, whereas if the viscosity is less than the reference value, no sediment will remain undissolved.
By removing the organic matter exceeding the above-mentioned reference value from the system, the concentrated organic deteriorated matter can be removed, and therefore the dissolution reaction in the sediment dissolution step S3 can be carried out efficiently.
以下、本発明の実施例を説明する。 The following describes an embodiment of the present invention.
＜実施例１＞
（不純物を含む有機溶媒の準備）
有機溶媒としては、抽出剤にカルボン酸系抽出剤であるトリノルマルオクチルアミン（以下、ＴＮＯＡという）を用い、これに希釈剤（丸善石油化学株式会社製、商品名：スワゾール１８００）を加えて２８重量％の抽出剤濃度に調整した。この抽出剤と希釈剤からなる有機溶媒を公知の方法を用いてコバルトの溶媒抽出処理に付すことを繰り返した。
Example 1
(Preparation of organic solvent containing impurities)
As the organic solvent, tri-n-octylamine (hereinafter referred to as TNOA), a carboxylic acid extractant, was used as the extractant, and a diluent (manufactured by Maruzen Petrochemical Co., Ltd., product name: Swazol 1800) was added to adjust the extractant concentration to 28% by weight. The organic solvent consisting of this extractant and diluent was repeatedly subjected to solvent extraction treatment of cobalt using a known method.
具体的な処理としては、図２に示す、ニッケルとコバルトを含有する原料を塩素ガスで浸出する浸出工程Ｓ１１に付しコバルトを含有する塩酸酸性溶液の抽出始液を得る。この抽出始液を溶媒抽出工程Ｓ１２に付す。溶媒抽出工程Ｓ１２では、ニッケルを抽出後液に残し、抽出後有機を得た。 As a specific process, as shown in FIG. 2, a raw material containing nickel and cobalt is subjected to a leaching process S11 in which chlorine gas is used to leach the raw material, and an extraction liquid of an acidic hydrochloric acid solution containing cobalt is obtained. This extraction liquid is then subjected to a solvent extraction process S12. In the solvent extraction process S12, nickel is left in the post-extraction liquid, and post-extraction organic matter is obtained.
次いで抽出後有機を公知の方法で洗浄し、逆抽出工程Ｓ１３に付した。逆抽出工程Ｓ１３で塩酸溶液を加えるとコバルトが逆抽出された逆抽出後液と逆抽後有機とに分離した。 The extracted organic matter was then washed using a known method and subjected to the back-extraction step S13. In the back-extraction step S13, a hydrochloric acid solution was added, and the cobalt was separated into the back-extraction liquid and the back-extraction organic matter.
逆抽出後有機には鉄や亜鉛などの金属系不純物や本発明の除去対象である有機系不純物が含有されるので、一部を抜き出し、図３に示す後処理工程に付した。 After stripping, the organic matter contained metal impurities such as iron and zinc, as well as the organic impurities that are the subject of removal in the present invention, so a portion of it was extracted and subjected to the post-treatment process shown in Figure 3.
後処理工程（図３）の亜鉛分離工程Ｓ１４では、逆抽出後有機に水酸化ナトリウムなどの中和剤を添加し、ｐＨを８～９に調整して中和し、澱物と一部の有機物の混合した分離後重液と有機物を主とする分離後軽液とに分離した。分離後軽液は塩酸を添加して活性化し、活性化後の有機溶媒はコバルト抽出に繰り返した。 In the zinc separation step S14 of the post-treatment process (Figure 3), a neutralizing agent such as sodium hydroxide was added to the organic solution after stripping, and the pH was adjusted to 8-9 for neutralization, and the organic solution was separated into a heavy liquid after separation, which was a mixture of sediment and some organic matter, and a light liquid after separation, which was mainly organic matter. The light liquid after separation was activated by adding hydrochloric acid, and the activated organic solvent was used again for cobalt extraction.
一方、分離後重液には塩酸を添加する澱液分離工程Ｓ１５に付し、分離後澱物溶解液と分離後澱物溶解後有機に固液分離した。金属系不純物が多く含まれる分離後澱物溶解液は排水処理工程に送り、公知の方法で排水処理して放出した。
分離後澱物溶解後有機は、逆抽出後有機と混合し有機溶媒として繰り返したり、亜鉛分離工程Ｓ１４に繰り返すことで、有機溶媒中に有機系不純物を蓄積させた。
On the other hand, the heavy liquid after separation was subjected to a starch liquid separation step S15 in which hydrochloric acid was added, and solid-liquid separation was performed into a separated sediment solution and a separated sediment solution after dissolving. The separated sediment solution containing a large amount of metal-based impurities was sent to a wastewater treatment step, where it was treated by a known method and released.
The organic solvent after separation and dissolution of the sediment was mixed with the organic solvent after stripping and used repeatedly as an organic solvent, or was repeated in the zinc separation step S14, thereby allowing organic impurities to accumulate in the organic solvent.
（基本工程による不純物除去）
まず、基本工程の硫酸洗浄工程Ｓ１に付した。準備しておいた有機系不純物を含有する有機溶媒（分離後澱物溶解後有機に相当）から５サンプルを分取した。
(Basic process for removing impurities)
First, the mixture was subjected to the sulfuric acid washing step S1, which is a basic step. Five samples were taken from the prepared organic solvent containing organic impurities (corresponding to the organic solvent after dissolving the sediment after separation).
（硫酸洗浄）
５サンプルのそれぞれを硫酸を含まない水だけの場合、濃度０．１ｍｏｌ／ｌ、０．５ｍｏｌ／ｌ、１ｍｏｌ／ｌ、２ｍｏｌ／ｌの硫酸溶液を有機溶媒と同じ体積だけ添加した場合で、硫酸洗浄した（硫酸洗浄工程Ｓ１）。得られた有機溶媒中の亜鉛、鉄、銅の各濃度を測定し、金属系不純物の変化を調査した。
(Sulfuric acid washing)
Each of the five samples was washed with sulfuric acid in the following cases: water containing no sulfuric acid, or sulfuric acid solutions with concentrations of 0.1 mol/l, 0.5 mol/l, 1 mol/l, and 2 mol/l were added in the same volume as the organic solvent (sulfuric acid washing step S1). The concentrations of zinc, iron, and copper in the resulting organic solvent were measured, and changes in metallic impurities were investigated.
図５に示すように、０．１ｍｏｌ／ｌ程度の硫酸濃度で洗浄することで、有機溶媒中の亜鉛と鉄と銅を低減することができた。洗浄前の有機中には亜鉛が７．９ｇ／Ｌ、鉄が１．８ｇ／Ｌ、銅が０．２９ｇ／Ｌ含有されていたが、いずれも目標値以下に低減できた。具体的には、亜鉛が５．５ｇ／Ｌ、鉄が０．１７g／Ｌ、銅が０．１４ｇ／Ｌに低減した。 As shown in Figure 5, by washing with a sulfuric acid concentration of about 0.1 mol/L, it was possible to reduce the zinc, iron, and copper in the organic solvent. Before washing, the organic solvent contained 7.9 g/L of zinc, 1.8 g/L of iron, and 0.29 g/L of copper, but all of these were reduced to below the target value. Specifically, zinc was reduced to 5.5 g/L, iron to 0.17 g/L, and copper to 0.14 g/L.
（アルカリ洗浄）
次いで、上記の硫酸洗浄を行った硫酸洗浄後有機を分取し、各サンプルごとに洗浄後の水相／有機相の体積比（Ｏ／Ａ比）が１．０となるように、水酸化ナトリウム溶液を添加して、温度を６０℃に維持しながら、それぞれｐＨを５から１２の範囲で調整し、アルカリ洗浄処理を行った（アルカリ洗浄工程Ｓ２）。
(Alkaline cleaning)
Next, the organic phase after the sulfuric acid washing was separated and each sample was subjected to an alkaline washing treatment by adding a sodium hydroxide solution so that the volume ratio of the aqueous phase to the organic phase after washing (O/A ratio) was 1.0, and adjusting the pH to a range of 5 to 12 while maintaining the temperature at 60° C. (alkaline washing step S2).
アルカリ洗浄処理前後の有機溶媒を、高速液体クロマトグラフ質量分析装置（ＬＣ／ＭＳ）を用いて測定し、検出成分のピーク面積比から各成分の有機溶媒から有機系不純物が除去された割合、すなわち洗浄率を求めた。 The organic solvent before and after the alkaline cleaning treatment was measured using a high-performance liquid chromatograph mass spectrometer (LC/MS), and the ratio of the peak areas of the detected components was used to determine the proportion of organic impurities removed from the organic solvent for each component, i.e., the cleaning rate.
アルカリ洗浄処理によるｐＨと有機系不純物の除去率（洗浄率）の関係を表１ならびに図６に示す。ｐＨが６で９％の洗浄率が得られるが、ｐＨをさらに８から９に上げることで洗浄率が線形で急激に向上していた。特に、ｐＨ９ではヘプタン酸（Ｃ７Ｈ１４Ｏ２）やトリクロロメタンスルホン酸（ＣＨＣｌ３Ｏ３Ｓ）やテトラクロロベンゼンスルホン酸（Ｃ６Ｈ２Ｃｌ４Ｏ３Ｓ）の洗浄率は８６％以上が得られた。 The relationship between pH and the removal rate (cleaning rate) of organic impurities by alkaline cleaning treatment is shown in Table 1 and Figure 6. A cleaning rate of 9% was obtained at a pH of 6, but the cleaning rate increased rapidly and linearly by further increasing the pH from 8 to 9. In particular, at pH 9 , a cleaning rate of 86% or more was obtained for heptanoic acid ( C7H14O2 ) , trichloromethanesulfonic acid ( CHCl3O3S ), and tetrachlorobenzenesulfonic acid ( C6H2Cl4O3S ) .
＜実施例２＞
有機系不純物だけを含有し、金属系不純物が含まれないＴＮＯＡを含む有機溶媒を処理対象として、本発明の基本工程により有機系不純物の除去を行い、結果を確認した。
Example 2
The organic solvent containing TNOA, which contains only organic impurities and does not contain metal impurities, was treated to remove the organic impurities according to the basic process of the present invention, and the results were confirmed.
具体的には、鉄や亜鉛を含まない塩化コバルト試薬を溶解した塩酸酸性溶液を抽出始液に用い、以降は実施例１と同じ方法で有機系不純物を有機溶媒中に蓄積させた。
有機系不純物が充分に蓄積した時点で、後処理工程（図３）の亜鉛分離工程Ｓ１４に付し、中和して分離後重液と分離後軽液を得た。そして分離後重液には塩酸で溶解する澱液分離工程Ｓ１５に付して分離後澱物溶解後有機を得た。この分離後澱物溶解後有機は有機系不純物を含んでいる。
Specifically, an acidic hydrochloric acid solution containing a cobalt chloride reagent not containing iron or zinc dissolved therein was used as the starting extraction liquid, and thereafter, the organic impurities were allowed to accumulate in the organic solvent in the same manner as in Example 1.
When the organic impurities have accumulated sufficiently, the zinc is separated in the zinc separation step S14 of the post-treatment process (Fig. 3), neutralized to obtain a heavy liquid and a light liquid. The heavy liquid is then dissolved in hydrochloric acid in the sediment separation step S15 to obtain an organic liquid after separation and dissolution of the sediment. This organic liquid after separation and dissolution of the sediment contains organic impurities.
ついで、分離後澱物溶解後有機を基本工程（図１）に付した。この分離後澱物溶解後有機は鉄や亜鉛を含んでいないので、硫酸洗浄工程Ｓ１は省略し、そのままアルカリ洗浄工程Ｓ２に付した。この段階の分離後澱物溶解後有機のヘプタン酸濃度は、ガスクロマトグラフ／水素炎イオン化検出器と高速液体クロマトグラフ質量分析装置を用いて測定すると、４８００重量ｐｐｍだった。なおＴＮＯＡ濃度は１８重量％だった。 Then, the separated sediment-dissolved organic was subjected to the basic process (Figure 1). Because this separated sediment-dissolved organic did not contain iron or zinc, the sulfuric acid washing process S1 was omitted and it was directly subjected to the alkali washing process S2. The heptanoic acid concentration of the separated sediment-dissolved organic at this stage was measured using a gas chromatograph/hydrogen flame ionization detector and a high-performance liquid chromatograph mass spectrometer, and was found to be 4,800 ppm by weight. The TNOA concentration was 18% by weight.
アルカリ洗浄工程Ｓ２では、分離後澱物溶解後有機に有機と同じ体積分の純水と水酸化ナトリウム溶液を加えて、温度６０℃に維持してｐＨ１２に調整した。次いで、遠心分離機を用いて有機溶媒である洗浄後軽液と洗浄後重液を分離し、洗浄後軽液に有機と同じ体積分の純水と水酸化ナトリウム溶液を添加してｐＨ１２に調整するアルカリ洗浄を繰り返し、合計４回アルカリ洗浄を行った。終了後のヘプタン酸は３０重量ｐｐｍまで減少した。ＴＮＯＡの濃度は２７重量％と最初に調合した濃度とほとんど同じであるので、濃縮や希釈による液量変化を加味しても、本発明の不純物除去方法を用いることでヘプタン酸等の有機系不純物を効果的に除去できることが確認された。 In the alkaline washing step S2, after the separation and dissolution of the sediment, the organic was added with the same volume of pure water and sodium hydroxide solution as the organic, and the temperature was maintained at 60°C to adjust the pH to 12. Next, a centrifuge was used to separate the post-wash light liquid, which is an organic solvent, from the post-wash heavy liquid, and the post-wash light liquid was added with the same volume of pure water and sodium hydroxide solution as the organic to adjust the pH to 12, repeating the alkaline washing four times in total. After completion, the heptanoic acid had decreased to 30 ppm by weight. Since the concentration of TNOA was 27% by weight, which was almost the same as the concentration initially prepared, it was confirmed that organic impurities such as heptanoic acid could be effectively removed by using the impurity removal method of the present invention, even when taking into account the change in the liquid volume due to concentration or dilution.
＜実施例３＞
（劣化評価）
劣化評価の適切な判断基準を得るため澱物溶解工程Ｓ３で得た澱物溶解後有機の粘度を測定し、粘度に対する澱物溶解工程Ｓ３への影響を確認した。
具体的には、実施例１の硫酸濃度０．１ｍｏｌ／ｌで洗浄（硫酸洗浄工程Ｓ１に対応）して得た硫酸洗浄後有機を水酸化ナトリウム溶液でｐＨ１２に調整し、アルカリ洗浄（アルカリ洗浄工程Ｓ２に対応）して洗浄後重液を得た。アルカリ洗浄後重液２２５ｍＬとアルカリ洗浄後軽液３０ｍＬの混合液に０．１ｍｏｌ／ｌ硫酸３３７ｍｌを添加し、１０ｍｏｌ／ｌ硫酸を用いてｐＨ０．８に調整（澱物溶解工程Ｓ３に対応）した。４０℃、１時間の攪拌後、有機粘度の測定と澱物の溶解状態を確認した。溶解後有機を全量回収し、この有機を再度アルカリ洗浄後重液２２５ｍＬと混合し１回目と同様に硫酸による澱物溶解を行った。上記の方法で６回澱物溶解を繰り返した。
Example 3
(Deterioration assessment)
In order to obtain an appropriate standard for evaluating deterioration, the viscosity of the organic solvent obtained in the sediment dissolving step S3 after dissolving the sediment was measured, and the effect of the sediment dissolving step S3 on the viscosity was confirmed.
Specifically, the sulfuric acid-washed organic obtained by washing with 0.1 mol/l sulfuric acid (corresponding to sulfuric acid washing step S1) in Example 1 was adjusted to pH 12 with sodium hydroxide solution, and then washed with alkali (corresponding to alkali washing step S2) to obtain a washed heavy liquid. 337 ml of 0.1 mol/l sulfuric acid was added to a mixture of 225 mL of the heavy liquid after alkali washing and 30 mL of the light liquid after alkali washing, and the pH was adjusted to 0.8 using 10 mol/l sulfuric acid (corresponding to sediment dissolution step S3). After stirring at 40°C for 1 hour, the organic viscosity was measured and the dissolution state of the sediment was confirmed. The entire amount of the dissolved organic was recovered, and this organic was mixed again with 225 mL of the heavy liquid after alkali washing, and sediment dissolution was performed with sulfuric acid in the same manner as the first time. Sediment dissolution was repeated six times by the above method.
結果を図７および図８に示す。図７は６回繰り返した澱物溶解に使用したビーカーの写真であり、溶解回数が１回から６回までを左から右に順に示している。図８は横軸に溶解回数をおき、縦軸に有機の粘度（単位ｍＰａ・ｓ）をおいている。
図７に示すように、溶解５回目で澱物の溶け残りが発生し、６回目でも有機相に未溶解の澱物が存在することが確認された。図８から分かるように溶解回数が増えるに従って有機の粘度は線形で高くなり、５回のときの有機の粘度は１６０ｍＰａ・ｓである。この結果から、有機の粘度が、１６０ｍＰａ・ｓ未満であると澱物の溶け残りは発生しないことが確認された。一方、有機の粘度が１６０ｍＰａ・ｓ以上では澱物の溶け残りが発生しており、有機の粘度が高くなり酸と澱物の接触を阻害していることが確認された。
The results are shown in Figures 7 and 8. Figure 7 is a photograph of the beaker used for dissolving the sediment six times, and the number of dissolutions is shown from left to right in order from 1 to 6. Figure 8 plots the number of dissolutions on the horizontal axis and the viscosity of the organic solvent (unit: mPa s) on the vertical axis.
As shown in Fig. 7, it was confirmed that residual sediment was generated after the fifth dissolution, and that undissolved sediment was present in the organic phase even after the sixth dissolution. As can be seen from Fig. 8, the viscosity of the organic increases linearly as the number of dissolutions increases, and the viscosity of the organic after the fifth dissolution is 160 mPa·s. From this result, it was confirmed that no residual sediment was generated when the viscosity of the organic was less than 160 mPa·s. On the other hand, residual sediment was generated when the viscosity of the organic was 160 mPa·s or more, and it was confirmed that the high viscosity of the organic hindered the contact between the acid and the sediment.
Ｓ１ 硫酸洗浄工程
Ｓ２ アルカリ洗浄工程
Ｓ３ 澱物溶解工程
Ｓ１１ 浸出工程
Ｓ１２ 溶媒抽出工程
Ｓ１３ 逆抽出工程
Ｓ１４ 亜鉛分離工程
Ｓ１５ 澱液分離工程
Ｓ２１ 粘性調整工程
Ｓ２２ 劣化評価工程
S1 Sulfuric acid washing step S2 Alkaline washing step S3 Sediment dissolving step S11 Leaching step S12 Solvent extraction step S13 Back extraction step S14 Zinc separation step S15 Sediment separation step S21 Viscosity adjustment step S22 Deterioration evaluation step
Claims (8)
（１）不純物を含む有機溶媒に、硫酸を添加して、硫酸洗浄後液と硫酸洗浄後有機を得る硫酸洗浄工程、
（２）前記硫酸洗浄後有機に中和剤を添加してｐＨを調整し、中和澱物と水相と有機相を有する洗浄後重液と有機相を含む洗浄後軽液に分離するアルカリ洗浄工程、
（３）前記洗浄後重液に、硫酸を添加し、澱物溶解後有機と澱物溶解液を得る澱物溶解工程からなり、
（４）前記澱物溶解後有機を前記アルカリ洗浄工程に繰り返すものであり、
（５）上記アルカリ洗浄工程の前に劣化評価工程を実行し、劣化程度が許容できると評価された前記澱物溶解後有機を前記アルカリ洗浄工程に付す
ことを特徴とする有機溶媒中の有機系不純物の除去方法。 A method for removing organic impurities from an organic solvent containing impurities, comprising the following basic steps (1) to (4):
(1) a sulfuric acid washing step in which sulfuric acid is added to an organic solvent containing impurities to obtain a sulfuric acid washed solution and a sulfuric acid washed organic;
(2) an alkali washing step in which a neutralizing agent is added to the organic phase after the sulfuric acid washing to adjust the pH and separate the organic phase into a post-wash heavy liquid having a neutralized precipitate, an aqueous phase, and an organic phase, and a post-wash light liquid having an organic phase;
(3) a sediment dissolving step of adding sulfuric acid to the post-wash heavy liquid to obtain an organic solvent and a sediment dissolution solution;
(4) After dissolving the sediment, the organic layer is returned to the alkaline washing step;
(5) A method for removing organic impurities in an organic solvent, comprising carrying out a deterioration evaluation step prior to the alkaline washing step, and subjecting the post-sediment dissolution organic solvent having an acceptable degree of deterioration to the alkaline washing step.
ニッケル、コバルト、亜鉛を含有する原料から溶媒抽出工程によりニッケルを含む抽出後液を分離して抽出後有機を得、
前記抽出後有機を逆抽出工程でコバルトを含む逆抽出後液を分離して得た逆抽後有機である
ことを特徴とする請求項１記載の有機溶媒中の有機系不純物の除去方法。 The organic solvent containing impurities subjected to the basic process is
A raw material containing nickel, cobalt, and zinc is subjected to a solvent extraction process to separate a post-extraction liquid containing nickel, thereby obtaining a post-extraction organic compound;
2. The method for removing organic impurities from an organic solvent according to claim 1, wherein the extracted organic solvent is a stripped organic solvent obtained by separating a stripped liquid containing cobalt in a stripping step.
ニッケルとコバルトと亜鉛を含有する原料を酸または塩素ガスで浸出する浸出工程で抽出始液を得、
次いで前記溶媒抽出工程と前記逆抽出工程を順に実行して得た逆抽後有機である
ことを特徴とする請求項２記載の有機溶媒中の有機系不純物の除去方法。 The organic solvent containing impurities subjected to the basic process is
A starting solution is obtained by leaching a raw material containing nickel, cobalt, and zinc with an acid or chlorine gas in a leaching process,
3. The method for removing organic impurities in an organic solvent according to claim 2, wherein the solvent extraction step and the stripping step are then carried out in sequence to obtain a stripped organic solvent.
前記逆抽出後有機に中和剤を添加し亜鉛を分離する亜鉛分離工程で、分離後重液と分離後軽液を得、
前記分離後重液に塩酸を添加して分離後澱物溶解液を分離する澱液分離工程で得た分離後澱物溶解後有機である
ことを特徴とする請求項２記載の有機溶媒中の有機系不純物の除去方法。 The organic solvent containing impurities subjected to the basic process is
In a zinc separation step in which a neutralizing agent is added to the organic solvent after the stripping to separate zinc, a heavy liquid after separation and a light liquid after separation are obtained,
3. The method for removing organic impurities in an organic solvent according to claim 2, wherein the separated starch-dissolved organic is obtained in a starch separation step in which hydrochloric acid is added to the separated heavy liquid to separate a separated starch-dissolved liquid.
ことを特徴とする請求項１記載の有機溶媒中の有機系不純物の除去方法。 2. The method for removing organic impurities in an organic solvent according to claim 1, wherein in the alkaline washing step, the pH of the organic solvent and the neutralizing agent mixed after the sulfuric acid washing is maintained in the range of 6 to 12.
ことを特徴とする請求項５記載の有機溶媒中の有機系不純物の除去方法。 6. The method for removing organic impurities in an organic solvent according to claim 5, wherein the neutralizing agent is added in the form of a solution or a slurry containing the neutralizing agent.
ことを特徴とする請求項１記載の有機溶媒中の有機系不純物の除去方法。 2. The method for removing organic impurities from an organic solvent according to claim 1, further comprising the step of subjecting the organic solvent containing the impurities to a viscosity adjusting step of adjusting the viscosity before subjecting the organic solvent containing the impurities to the basic step.
ことを特徴とする請求項１記載の有機溶媒中の有機系不純物の除去方法。 2. The method for removing organic impurities in an organic solvent according to claim 1, wherein the deterioration evaluation criterion in the deterioration evaluation step is that the viscosity of the organic solvent after dissolving the sediment is less than 160 mPa·s.
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