JP2024005489A - Method for purifying anionic surface active agent - Google Patents
Method for purifying anionic surface active agent Download PDFInfo
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- JP2024005489A JP2024005489A JP2022105689A JP2022105689A JP2024005489A JP 2024005489 A JP2024005489 A JP 2024005489A JP 2022105689 A JP2022105689 A JP 2022105689A JP 2022105689 A JP2022105689 A JP 2022105689A JP 2024005489 A JP2024005489 A JP 2024005489A
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- exchange resin
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- acidic cation
- anionic surfactant
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- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000004094 surface-active agent Substances 0.000 title abstract description 9
- 125000000129 anionic group Chemical group 0.000 title abstract 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 103
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 59
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 50
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 50
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 239000003945 anionic surfactant Substances 0.000 claims description 57
- 230000002378 acidificating effect Effects 0.000 claims description 53
- 239000003957 anion exchange resin Substances 0.000 claims description 29
- 238000000746 purification Methods 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000013522 chelant Chemical group 0.000 claims description 8
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 abstract description 9
- 125000002091 cationic group Chemical group 0.000 abstract description 4
- 150000001455 metallic ions Chemical class 0.000 abstract 3
- 239000000243 solution Substances 0.000 description 35
- 229910021645 metal ion Inorganic materials 0.000 description 29
- 238000005342 ion exchange Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- -1 alkali metal salt Chemical class 0.000 description 14
- 229920001429 chelating resin Polymers 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229920002125 Sokalan® Polymers 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 5
- 229940023913 cation exchange resins Drugs 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- LQNRPMPBDYBWMW-UHFFFAOYSA-N 2-aminoethanol;dodecyl dihydrogen phosphate Chemical compound NCCO.CCCCCCCCCCCCOP(O)(O)=O LQNRPMPBDYBWMW-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical class C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UMITUPPOTYGICT-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid ethanol Chemical compound CCO.CCO.CCO.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O UMITUPPOTYGICT-UHFFFAOYSA-N 0.000 description 1
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- MGDNLGRMXPBCOR-UHFFFAOYSA-N bis(2-hydroxyethyl)azanium;dodecanoate Chemical compound OCCNCCO.CCCCCCCCCCCC(O)=O MGDNLGRMXPBCOR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- AXAURZWPEBQDNG-UHFFFAOYSA-N hexadecanoate;2-hydroxyethylazanium Chemical class NCCO.CCCCCCCCCCCCCCCC(O)=O AXAURZWPEBQDNG-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- ZHALDANPYXAMJF-UHFFFAOYSA-N octadecanoate;tris(2-hydroxyethyl)azanium Chemical class OCC[NH+](CCO)CCO.CCCCCCCCCCCCCCCCCC([O-])=O ZHALDANPYXAMJF-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BYKRNSHANADUFY-UHFFFAOYSA-M sodium octanoate Chemical compound [Na+].CCCCCCCC([O-])=O BYKRNSHANADUFY-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Treatment Of Liquids With Adsorbents In General (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Description
本開示は、アニオン界面活性剤の精製方法に関する。 The present disclosure relates to a method for purifying anionic surfactants.
電子部品や半導体等のデバイスの製造及び精密加工の技術分野などにおいて、界面活性剤を含有した高機能洗浄剤が使用されている。シリコンウエハーや半導体などの製造工程において生じる恐れのある汚染物質や付着物には、パーティクルと呼ばれるゴミや塵埃、種々の金属イオンなどが挙げられる。半導体上にパーティクルがあると、回路が断線するなどして、不良動作を起こしてしまう。その結果、半導体が使用できなくなり、製品の歩留まりが低下する。また、半導体の金属配線上に金属イオンがのっていると、電流が漏れて半導体が正常に動作しなくなるという事態が起こり得る。金属イオンの存在は、電気的特性の変動に起因する不十分な性能など、製造されたデバイスに対して重大な問題を呈する可能性がある。このように、パーティクルの存在は、半導体の品質に著しく影響を及ぼす。さらに、近年はスマートフォンやパソコン等のデバイスの小型化が目覚ましく、それらに使用される半導体についても小型化が進んでいる。小型化された半導体は、回路の線幅が細くなっており、より小さなパーティクルによって回路の変形等が起こるため、より高い精度のパーティクル除去が必要となる。そのため、金属イオンの濃度をより低減した、精製度の高い界面活性剤が望まれている。 High-performance cleaning agents containing surfactants are used in the technical fields of manufacturing and precision processing of devices such as electronic parts and semiconductors. Contaminants and deposits that may be generated in the manufacturing process of silicon wafers, semiconductors, etc. include dirt and dust called particles, and various metal ions. If particles are present on the semiconductor, the circuit may break or otherwise malfunction. As a result, the semiconductor becomes unusable and the yield of products decreases. Further, if metal ions are placed on the metal wiring of a semiconductor, a situation may occur in which current leaks and the semiconductor does not operate normally. The presence of metal ions can present significant problems to manufactured devices, such as poor performance due to variations in electrical properties. Thus, the presence of particles significantly affects the quality of semiconductors. Furthermore, in recent years, devices such as smartphones and personal computers have become significantly smaller, and the semiconductors used in these devices have also become smaller. In miniaturized semiconductors, the line width of circuits has become narrower, and smaller particles can cause deformation of the circuits, so it is necessary to remove particles with higher precision. Therefore, a highly purified surfactant with a lower metal ion concentration is desired.
従来から、アニオン界面活性剤の精製方法については、一般的な濃縮、晶析、抽出による方法の他に、限外濾過膜を用いて濾過する方法（例えば特許文献１参照）や、イオン交換膜を用いた電気透析により精製する方法（例えば特許文献２参照）等が知られている。 Conventionally, methods for purifying anionic surfactants include, in addition to general methods of concentration, crystallization, and extraction, a method of filtration using an ultrafiltration membrane (see, for example, Patent Document 1), and a method of filtration using an ion exchange membrane. A method of purifying by electrodialysis using (for example, see Patent Document 2) is known.
また、有機スルホン酸のアルカリ金属塩を、強酸性カチオン交換樹脂を用いたイオン交換法に供して処理することにより、各種の金属イオン濃度を低減させる方法（例えば特許文献３参照）が知られている。 Furthermore, a method is known in which the concentration of various metal ions is reduced by subjecting an alkali metal salt of an organic sulfonic acid to an ion exchange method using a strongly acidic cation exchange resin (see, for example, Patent Document 3). There is.
しかし、特許文献１又は特許文献２に開示されている濾過膜やイオン交換膜を用いた方法では、アニオン界面活性剤溶液が含有する金属イオン濃度を十分に低減すること、具体的には、金属イオン濃度を各種の金属イオン毎で数ｐｐｂの単位にまで低減することが難しいという問題がある。 However, in the method using a filtration membrane or ion exchange membrane disclosed in Patent Document 1 or Patent Document 2, it is necessary to sufficiently reduce the concentration of metal ions contained in the anionic surfactant solution. There is a problem in that it is difficult to reduce the ion concentration of each metal ion to a level of several ppb.
また、一部のアニオン界面活性剤は、金属塩や有機アミン塩などの状態では水溶性であるが、親水基がＨ＋（プロトン）と結合した酸型の状態では水に対する溶解度が著しく低下し、非水溶性となる。このような酸型で非水溶性となるアニオン界面活性剤を特許文献３に開示のイオン交換法で精製すると、金属イオンと強酸性カチオン交換樹脂のＨ＋とが交換反応し、金属イオンは低減できるものの、アニオン界面活性剤が酸型になって析出してしまい、精製を行うことが出来ない。 In addition, some anionic surfactants are water-soluble in the form of metal salts or organic amine salts, but their solubility in water decreases significantly in the acid form in which the hydrophilic group is bonded to H + (protons). , it becomes water-insoluble. When such acid-type, water-insoluble anionic surfactants are purified by the ion exchange method disclosed in Patent Document 3, metal ions and H + of the strongly acidic cation exchange resin undergo an exchange reaction, and metal ions are reduced. Although it is possible, the anionic surfactant becomes acidic and precipitates, making purification impossible.
そこで本開示は、アニオン界面活性剤について、精製途中で析出を起こすことなく、金属イオンを効率よく低減する精製方法を提供する。 Therefore, the present disclosure provides a purification method for efficiently reducing metal ions of an anionic surfactant without causing precipitation during purification.
上記課題を解決するため、本開示の技術は以下の手段をとる。
［１］強酸性カチオン交換樹脂を含むイオン交換樹脂にアルカリ成分を接触させる接触工程１と、前記接触工程１で得られたイオン交換樹脂にアニオン界面活性剤を接触させる接触工程２と、を含むことを特徴とするアニオン界面活性剤の精製方法。
［２］前記イオン交換樹脂が、強酸性カチオン交換樹脂のみからなる［１］に記載の精製方法。
［３］前記イオン交換樹脂が、強酸性カチオン交換樹脂と、強塩基性アニオン交換樹脂、弱塩基性アニオン交換樹脂、弱酸性カチオン交換樹脂、及びキレート交換樹脂から選ばれる少なくとも１つと、の混合樹脂である［１］に記載の精製方法。
［４］前記接触工程１が、強酸性カチオン交換樹脂を含むイオン交換樹脂にアルカリ成分を接触させた後に、更に強塩基性アニオン交換樹脂、弱塩基性アニオン交換樹脂、弱酸性カチオン交換樹脂、及びキレート交換樹脂から選ばれる少なくとも１つを混合させる工程１－１を含む［１］に記載の精製方法。
［５］前記アニオン界面活性剤が、ＨＬＢが２０以下の酸成分の中和塩である請求項［１］～［４］のいずれかに記載の精製方法。
［６］前記アルカリ成分が、有機アミン、４級アンモニウム塩、及びアンモニアから選ばれる少なくとも1つである［１］～［４］のいずれかに記載の精製方法。
［７］前記アルカリ成分が、有機アミン、４級アンモニウム塩、及びアンモニアから選ばれる少なくとも1つである［５］に記載の精製方法。
In order to solve the above problems, the technology of the present disclosure takes the following measures.
[1] Includes a contact step 1 in which an alkali component is brought into contact with an ion exchange resin containing a strongly acidic cation exchange resin, and a contact step 2 in which an anionic surfactant is brought into contact with the ion exchange resin obtained in the contact step 1. A method for purifying an anionic surfactant, characterized by:
[2] The purification method according to [1], wherein the ion exchange resin comprises only a strongly acidic cation exchange resin.
[3] The ion exchange resin is a mixed resin of a strongly acidic cation exchange resin and at least one selected from a strongly basic anion exchange resin, a weakly basic anion exchange resin, a weakly acidic cation exchange resin, and a chelate exchange resin. The purification method according to [1].
[4] After the contacting step 1 brings the alkaline component into contact with the ion exchange resin containing the strongly acidic cation exchange resin, the contacting step 1 further includes a strongly basic anion exchange resin, a weakly basic anion exchange resin, a weakly acidic cation exchange resin, and The purification method according to [1], which includes step 1-1 of mixing at least one selected from chelate exchange resins.
[5] The purification method according to any one of claims [1] to [4], wherein the anionic surfactant is a neutralized salt of an acid component having an HLB of 20 or less.
[6] The purification method according to any one of [1] to [4], wherein the alkaline component is at least one selected from organic amines, quaternary ammonium salts, and ammonia.
[7] The purification method according to [5], wherein the alkaline component is at least one selected from organic amines, quaternary ammonium salts, and ammonia.
なお、本明細書において「Ａ～Ｂ」で示される数値範囲は、特段の記載が無い限り、その上限及び下限を含む。つまり、「Ａ～Ｂ」は「Ａ以上、Ｂ以下」を意味する。 In this specification, the numerical range indicated by "A to B" includes its upper and lower limits, unless otherwise specified. In other words, "A to B" means "A or more and B or less".
以上説明した本開示の精製方法によれば、処理途中で析出を起こすことなく、アニオン界面活性剤から金属イオンを効率よく低減することができる。 According to the purification method of the present disclosure described above, metal ions can be efficiently reduced from an anionic surfactant without causing precipitation during treatment.
本開示のアニオン界面活性剤の精製方法は、イオン交換法による。強酸性カチオン交換樹脂を含むイオン交換樹脂にアルカリ成分を接触させる接触工程１と、前記接触工程１で得られたイオン交換樹脂にアニオン界面活性剤を接触させる接触工程２と、を含む。 The method for purifying the anionic surfactant of the present disclosure is based on an ion exchange method. The method includes a contact step 1 in which an alkali component is brought into contact with an ion exchange resin including a strongly acidic cation exchange resin, and a contact step 2 in which an anionic surfactant is brought into contact with the ion exchange resin obtained in the contact step 1.
≪接触工程１≫
接触工程１は、強酸性カチオン交換樹脂を含むイオン交換樹脂にアルカリ成分を接触させる工程である。イオン交換樹脂にアルカリ成分を接触させることにより、アルカリ成分由来のカチオン成分をイオン交換樹脂が含む強酸性カチオン交換樹脂に吸着させることができる。接触工程１は後述する工程１－１を含んでもよい。
≪Contact process 1≫
Contact step 1 is a step of bringing an alkali component into contact with an ion exchange resin including a strongly acidic cation exchange resin. By bringing the alkali component into contact with the ion exchange resin, the cation component derived from the alkali component can be adsorbed onto the strongly acidic cation exchange resin contained in the ion exchange resin. Contact step 1 may include step 1-1 described below.
＜イオン交換樹脂＞
イオン交換樹脂は、強酸性カチオン交換樹脂を含んでいればよく、強酸性カチオン交換樹脂のみで構成されていてもよいし、強酸性カチオン交換樹脂と他のイオン交換樹脂との混合樹脂であってもよい。他のイオン交換樹脂としては、弱酸性カチオン交換樹脂、強塩基性アニオン交換樹脂、弱塩基性アニオン交換樹脂、キレート交換樹脂等が挙げられ、これらは１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。各イオン交換樹脂の種類としては特に限定されず、公知のものを用いることができる。イオン交換樹脂の形状は、粒状に限定されることはなく、粉状、繊維状あるいは膜状でもかまわない。イオン交換樹脂の構造は、ゲル型であっても、マクロポーラス型であってもよい。
<Ion exchange resin>
The ion exchange resin only needs to contain a strongly acidic cation exchange resin, and may be composed only of a strongly acidic cation exchange resin, or may be a mixed resin of a strongly acidic cation exchange resin and another ion exchange resin. Good too. Examples of other ion exchange resins include weakly acidic cation exchange resins, strongly basic anion exchange resins, weakly basic anion exchange resins, and chelate exchange resins. You may use a combination of two or more species. The type of each ion exchange resin is not particularly limited, and known ones can be used. The shape of the ion exchange resin is not limited to granules, and may be powder, fiber, or film. The structure of the ion exchange resin may be a gel type or a macroporous type.
なお、イオン交換樹脂が、強酸性カチオン交換樹脂と強塩基性アニオン交換樹脂との組合せ、又は、強酸性カチオン交換樹脂と弱塩基性アニオン交換樹脂との組合せの場合には、金属イオンだけでなく不純物の陰イオンをも低減することができる。また、強酸性カチオン交換樹脂と弱酸性カチオン交換樹脂の組合せ、又は、強酸性カチオン交換樹脂とキレート樹脂の組合せの場合には、特定の金属イオンや多価金属イオンを除去することもできる。 In addition, when the ion exchange resin is a combination of a strongly acidic cation exchange resin and a strongly basic anion exchange resin, or a combination of a strongly acidic cation exchange resin and a weakly basic anion exchange resin, not only metal ions but also metal ions can be used. Impurity anions can also be reduced. Furthermore, in the case of a combination of a strongly acidic cation exchange resin and a weakly acidic cation exchange resin, or a combination of a strongly acidic cation exchange resin and a chelate resin, specific metal ions and polyvalent metal ions can also be removed.
強酸性カチオン交換樹脂とは、カチオン成分に対する吸着力が比較的高いカチオン交換樹脂であり、スルホン酸基（Ｒ－ＳＯ３ －Ｈ＋）等の強酸性交換基を官能基として持つものである。強酸性カチオン交換樹脂としては、例えば、アンバーライト（登録商標、以下同様）ＩＲ１２０Ｂ、ＩＲ１２４、２００ＣＴ（共に米国デュポン社製）、デュオライト（登録商標、以下同様）Ｃ２０、Ｃ２１ＬＦ、Ｃ２５５ＬＦＨ（共に米国デュポン社製）、ダイヤイオン（登録商標、以下同様）ＳＫ１０４Ｈ、ＳＫ１１０、ＳＫ１Ｂ（共に三菱ケミカル社製）等を使用できる。 A strongly acidic cation exchange resin is a cation exchange resin that has a relatively high adsorption power for cation components, and has a strong acid exchange group such as a sulfonic acid group (R-SO 3 − H + ) as a functional group. Strongly acidic cation exchange resins include, for example, Amberlite (registered trademark, hereinafter the same) IR120B, IR124, 200CT (both manufactured by DuPont, USA), Duolite (registered trademark, hereinafter the same) C20, C21LF, C255LFH (both manufactured by DuPont, USA) SK104H, SK110, SK1B (both manufactured by Mitsubishi Chemical Corporation), etc. can be used.
弱酸性カチオン交換樹脂は、カチオン成分に対する吸着力が比較的低いカチオン交換樹脂であり、カルボン酸基（Ｒ－ＣＯＯ－Ｈ＋）等の弱酸性交換基を官能基として持つものである。弱酸性カチオン交換樹脂としては、例えば、アンバーライト ＩＲＣ７６、ＨＰＲ８４００（共に米国デュポン社製）、デュオライト Ｃ４７６（米国デュポン社製）ダイヤイオン ＷＫ１０、ＷＫ１１（共に三菱ケミカル社製）等を使用できる。 The weakly acidic cation exchange resin is a cation exchange resin that has a relatively low adsorption power for cation components, and has a weakly acidic exchange group such as a carboxylic acid group (R-COO − H + ) as a functional group. As the weakly acidic cation exchange resin, for example, Amberlite IRC76, HPR8400 (both manufactured by DuPont, USA), Duolite C476 (both manufactured by DuPont, USA), Diaion WK10, WK11 (both manufactured by Mitsubishi Chemical), etc. can be used.
強塩基性アニオン交換樹脂とは、第４級アンモニウム塩基（Ｒ－Ｎ＋Ｒ１Ｒ２Ｒ３）等の強塩基性官能基が導入されたアニオン交換樹脂である。強塩基性アニオン交換樹脂としては、例えば、アンバーライト ＩＲＡ４００Ｊ、ＩＲＡ４０２ＢＬ、ＩＲＡ９００Ｊ（共に米国デュポン社製）、デュオライト Ａ１１３ＬＦ、Ａ１６１ＪＣＬ（共に米国デュポン社製）、ダイヤイオン ＳＡ１０Ａ、ＳＡ１１Ａ（共に三菱ケミカル社製）等のＩ型強塩基性アニオン交換樹脂、アンバーライト ＩＲＡ４１０Ｊ、ＩＲＡ９１０ＣＴ、ＨＰＲ４０１０（共に米国デュポン社製）、デュオライト Ａ１１６、Ａ１６２ＬＦ（共に米国デュポン社製）、ダイヤイオン ＳＡ２０Ａ、ＳＡ２０ＡＬＬ（共に三菱ケミカル社製）等のＩＩ型強塩基性アニオン交換樹脂を使用できる。 The strongly basic anion exchange resin is an anion exchange resin into which a strong basic functional group such as a quaternary ammonium base (RN + R 1 R 2 R 3 ) is introduced. Strongly basic anion exchange resins include, for example, Amberlite IRA400J, IRA402BL, IRA900J (both manufactured by DuPont, USA), Duolite A113LF, A161JCL (both manufactured by DuPont, USA), Diaion SA10A, SA11A (both manufactured by Mitsubishi Chemical) ), Amberlite IRA410J, IRA910CT, HPR4010 (both manufactured by DuPont, USA), Duolite A116, A162LF (both manufactured by DuPont, USA), Diaion SA20A, SA20ALL (both manufactured by Mitsubishi Chemical) Type II strongly basic anion exchange resins such as those manufactured by Co., Ltd.) can be used.
弱塩基性アニオン交換樹脂は、第１～３級アミン等の弱塩基性官能基が導入されたアニオン交換樹脂である。弱塩基性アニオン交換樹脂としては、例えば、アンバーライト ＩＲＡ６７、ＩＲＡ９６ＳＢ、ＩＲＡ９８（共に米国デュポン社製）、デュオライト Ａ３６８ＭＳ、Ａ３７８Ｄ、Ａ３７５ＬＦ（共に米国デュポン社製）、ダイヤイオン ＷＡ１０、ＷＡ２０（共に三菱ケミカル社製）等を使用できる。 The weakly basic anion exchange resin is an anion exchange resin into which a weakly basic functional group such as a primary to tertiary amine is introduced. Examples of weakly basic anion exchange resins include Amberlite IRA67, IRA96SB, and IRA98 (both manufactured by DuPont, USA), Duolite A368MS, A378D, and A375LF (both manufactured by DuPont, USA), and Diaion WA10 and WA20 (both manufactured by Mitsubishi Chemical). You can use products such as those manufactured by
キレート樹脂としては、例えば、アンバーライト ＩＲＣ７４７ＵＰＳ、ＩＲＣ７４８（共に米国デュポン社製）、デュオライト Ｃ４６７（米国デュポン社製）、ダイヤイオン ＣＲ１１、ＣＲ２０（共に三菱ケミカル社製）等を使用できる。 As the chelate resin, for example, Amberlite IRC747UPS, IRC748 (both manufactured by DuPont, USA), Duolite C467 (made by DuPont, USA), Diaion CR11, CR20 (both manufactured by Mitsubishi Chemical), etc. can be used.
強酸性カチオン交換樹脂および弱酸性カチオン交換樹脂は、予め塩酸や硫酸等の酸を用いて対イオンをＨ型とし、イオン交換水や超純水等で十分洗浄するなどして使用するのが好ましい。また、後述する接触工程２により金属イオンを吸着した後には、イオン交換樹脂はアルカリ金属型となっているが、上記と同様の操作によりＨ型に再生して使用することができる。 For strongly acidic cation exchange resins and weakly acidic cation exchange resins, it is preferable to use an acid such as hydrochloric acid or sulfuric acid to change the counterion to H type in advance, and wash thoroughly with ion-exchanged water, ultrapure water, etc. before use. . Furthermore, after adsorbing metal ions in contact step 2, which will be described later, the ion exchange resin is in an alkali metal type, but it can be regenerated into an H type and used by the same operation as described above.
強塩基性アニオン交換樹脂および弱塩基性アニオン交換樹脂は、予めテトラメチルアンモニウム塩水溶液等の塩を用いて対イオンをＯＨ型とし、イオン交換水や超純水等で十分洗浄するなどして使用するのが好ましい。また、カチオン交換樹脂の場合と同様に、ＯＨ型に再生したものを使用することができる。 For strongly basic anion exchange resins and weakly basic anion exchange resins, use a salt such as a tetramethylammonium salt aqueous solution to convert the counterion into OH type, and wash thoroughly with ion-exchanged water, ultrapure water, etc. before use. It is preferable to do so. Further, as in the case of cation exchange resins, those regenerated into OH type can be used.
＜アルカリ成分＞
イオン交換樹脂に接触させるアルカリ成分としては、公知のものであればよく、例えば、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、エチルアミン、ジエチルアミン、トリエチルアミン等の有機アミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、トリメチル(２－ヒドロキシエチル)アンモニウムヒドロキシド等の４級アンモニウム塩、アンモニア等が挙げられる。アルカリ成分は、例えばイオン交換能の観点から、有機アミン、４級アンモニウム塩、アンモニアが好ましく、有機アミン、アンモニアがより好ましく、有機アミンが更に好ましい。これらのアルカリ成分は、１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。
<Alkaline component>
The alkaline component to be brought into contact with the ion exchange resin may be any known one, such as organic amines such as monoethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, and triethylamine, tetramethylammonium hydroxide, and tetraethylammonium hydroxyl. Examples include quaternary ammonium salts such as tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethyl(2-hydroxyethyl)ammonium hydroxide, and ammonia. The alkali component is preferably an organic amine, a quaternary ammonium salt, or ammonia, more preferably an organic amine or ammonia, and even more preferably an organic amine, from the viewpoint of ion exchange ability. These alkaline components may be used alone or in combination of two or more.
＜アルカリ成分の接触方法＞
接触工程１においてイオン交換樹脂にアルカリ成分を接触させる方法は特に限定はなく、カラム法でも、バッチ法でもよい。作業効率などの観点から、カラム法が好ましい。強酸性カチオン交換樹脂と他のイオン交換樹脂をカラム法で組み合わせて使用する場合は、複層又は混合のいずれの系でも使用できる。イオン交換カラムなどの公知の装置は、本開示の方法に従ってアルカリ成分液をイオン交換樹脂に接触させるために用いることができる。
<Method of contacting alkaline components>
The method of bringing the alkali component into contact with the ion exchange resin in contact step 1 is not particularly limited, and may be a column method or a batch method. From the viewpoint of work efficiency, etc., the column method is preferable. When a strongly acidic cation exchange resin and another ion exchange resin are used in combination in a column method, either a multilayer system or a mixed system can be used. Known equipment such as ion exchange columns can be used to contact the alkaline component liquid with the ion exchange resin according to the methods of the present disclosure.
アルカリ成分液をイオン交換樹脂に接触させてイオン交換処理する際の空間速度（ＳＶ）は、０．０１～６．０ｈ－１とするのが好ましく、０．１～６．０ｈ－１とするのがより好ましい。 The space velocity (SV) when bringing the alkaline component liquid into contact with the ion exchange resin for ion exchange treatment is preferably 0.01 to 6.0 h -1 , and 0.1 to 6.0 h -1 . is more preferable.
≪工程１－１≫
工程１－１は、強酸性カチオン交換樹脂を含むイオン交換樹脂にアルカリ成分を接触させた後に、更に強塩基性アニオン交換樹脂、弱塩基性アニオン交換樹脂、弱酸性カチオン交換樹脂、及びキレート交換樹脂から選ばれる少なくとも１つ（すなわち、強酸性カチオン交換樹を含まないイオン交換樹脂）をイオン交換樹脂に混合させる工程である。接触工程１は、イオン交換樹脂にアルカリ成分を接触させて、強酸性カチオン交換樹脂にアルカリ成分由来のカチオン成分を吸着させることを目的とする。そのため、強酸性カチオン交換樹脂と強酸性カチオン交換樹脂以外のイオン交換樹脂を併用する場合、イオン交換樹脂はアルカリ成分との接触前に混合されてもよいし、工程１－１のように強酸性カチオン交換樹脂を含むイオン交換樹脂をアルカリ成分と接触させた後に、強酸性カチオン交換樹脂を含まないイオン交換樹脂と混合されてもよい。
≪Process 1-1≫
In step 1-1, after bringing an alkaline component into contact with an ion exchange resin containing a strongly acidic cation exchange resin, a strong basic anion exchange resin, a weakly basic anion exchange resin, a weakly acidic cation exchange resin, and a chelate exchange resin are further added. This is a step of mixing at least one selected from the following (that is, an ion exchange resin that does not contain a strongly acidic cation exchange resin) with an ion exchange resin. The purpose of the contact step 1 is to bring the ion exchange resin into contact with the alkaline component and to cause the strongly acidic cation exchange resin to adsorb the cation component derived from the alkaline component. Therefore, when using a strongly acidic cation exchange resin and an ion exchange resin other than the strongly acidic cation exchange resin, the ion exchange resin may be mixed before contacting with the alkaline component, or the strongly acidic cation exchange resin may be mixed before contacting with the alkaline component, or After the ion exchange resin containing the cation exchange resin is brought into contact with the alkaline component, it may be mixed with the ion exchange resin that does not contain the strongly acidic cation exchange resin.
≪接触工程２≫
接触工程２は、接触工程１で得られたイオン交換樹脂にアニオン界面活性剤を接触させる工程である。接触工程１でアルカリ成分を接触させたイオン交換樹脂にアニオン界面活性剤溶液を通液すると、溶液中の金属イオンがＨ＋ではなくカチオン成分に交換される。その結果、アニオン界面活性剤は水溶性の中和塩を形成することができるため、アニオン界面活性剤の析出や分離が発生することなく、溶液中の金属イオンを低減することが可能となる。
≪Contact process 2≫
Contact step 2 is a step in which the ion exchange resin obtained in contact step 1 is brought into contact with an anionic surfactant. When the anionic surfactant solution is passed through the ion exchange resin that has been contacted with the alkali component in contacting step 1, the metal ions in the solution are exchanged into cationic components instead of H + . As a result, since the anionic surfactant can form a water-soluble neutralized salt, it is possible to reduce metal ions in the solution without precipitation or separation of the anionic surfactant.
＜アニオン界面活性剤溶液＞
アニオン界面活性剤溶液は、イオン交換水等のイオン交換法に適した溶媒にアニオン界面活性剤を溶解した溶液である。
<Anionic surfactant solution>
The anionic surfactant solution is a solution in which an anionic surfactant is dissolved in a solvent suitable for the ion exchange method, such as ion exchanged water.
＜アニオン界面活性剤＞
アニオン界面活性剤としては、特に制限はなく公知のものであればよい。アニオン界面活性剤溶液中に含まれる金属イオンの量や、イオン交換水等に対する溶解性の観点から、アニオン界面活性剤は対塩基との中和塩であることが好ましい。
<Anionic surfactant>
The anionic surfactant is not particularly limited and may be any known one. From the viewpoint of the amount of metal ions contained in the anionic surfactant solution and the solubility in ion-exchanged water, the anionic surfactant is preferably a neutralized salt with a base.
対塩基としては、特に制限はなく、公知のものであればよい。例えば、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、エチルアミン、ジエチルアミン、トリエチルアミン等の有機アミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド等の４級アンモニウム塩、アンモニア、水酸化ナトリウム等が挙げられる。これらの対塩基は、１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。 The pair base is not particularly limited and may be any known one. For example, organic amines such as monoethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , ammonia, sodium hydroxide and the like. These pair bases may be used alone or in combination of two or more.
対塩基との中和塩である界面活性剤としては、例えば、（１）ラウリルリン酸モノエタノールアミン塩、ポリオキシエチレン（ＥＯ２）ラウリルリン酸モノエタノールアミン塩、ポリオキシエチレン（ＥＯ４）ラウリルエーテルリン酸ナトリウム、ポリオキシエチレン（ＥＯ３）アルキル（Ｃ１２－１５）エーテルリン酸アンモニウム塩等のリン酸塩、（２）アルキルジフェニルエーテルジスルホン酸トリエタノールアミン塩、アルキルスルホン酸ナトリウム、ドデシルベンゼンスルホン酸トリエタノールアミン塩等の有機スルホン酸塩、（３）ポリオキシエチレン（ＥＯ３）トリデシルエーテルカルボン酸モノエタノールアミン塩、オクタン酸ナトリウム等のカルボン酸塩、（４）ラウリン酸ジエタノールアミン塩、パルミチン酸モノエタノールアミン塩、ステアリン酸トリエタノールアミン塩等の脂肪酸塩、（５）スチレン／マレイン酸共重合物アンモニウム塩、ジアリルアミン／マレイン酸共重合物アンモニウム塩、ポリアクリル酸ナトリウム塩、ポリメタクリル酸ナトリウム塩、アクリル酸－メタクリル酸共重合物のナトリウム塩、イソブチレン－マレイン酸共重合物のナトリウム塩、メトキシＰＥＧグラフトポリメタクリル酸ナトリウム塩等が挙げられる。これらの化合物は、１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。 Examples of surfactants that are neutralized salts with counter bases include (1) lauryl phosphate monoethanolamine salt, polyoxyethylene (EO2) lauryl phosphate monoethanolamine salt, and polyoxyethylene (EO4) lauryl ether. Phosphates such as sodium phosphate, polyoxyethylene (EO3) alkyl (C12-15) ether ammonium phosphate, (2) alkyldiphenyl ether disulfonic acid triethanolamine salt, sodium alkyl sulfonate, dodecylbenzenesulfonic acid triethanol Organic sulfonates such as amine salts, (3) polyoxyethylene (EO3) tridecyl ether carboxylic acid monoethanolamine salts, carboxylates such as sodium octoate, (4) diethanolamine laurate, monoethanolamine palmitate salts, fatty acid salts such as stearic acid triethanolamine salts, (5) styrene/maleic acid copolymer ammonium salts, diallylamine/maleic acid copolymer ammonium salts, polyacrylic acid sodium salts, polymethacrylic acid sodium salts, acrylic acid Examples include sodium salt of -methacrylic acid copolymer, sodium salt of isobutylene-maleic acid copolymer, and methoxyPEG-grafted polymethacrylic acid sodium salt. These compounds may be used alone or in combination of two or more.
本開示に用いるアニオン界面活性剤は、例えば水溶性の観点から、有機概念図の計算式によるＨＬＢが２０以下である酸成分の中和塩であることが好ましく、ＨＬＢが１５以下であることがより好ましい。なお、アニオン界面活性剤の酸成分とは、アニオン界面活性剤の親水基がＨ＋と結合した酸型の状態を意味する。 The anionic surfactant used in the present disclosure is preferably a neutralized salt of an acid component having an HLB of 20 or less according to the organic conceptual diagram calculation formula, for example from the viewpoint of water solubility, and preferably has an HLB of 15 or less. More preferred. Note that the acid component of the anionic surfactant means an acid type state in which the hydrophilic group of the anionic surfactant is bonded to H + .
＜ＨＬＢの算出方法＞
本開示におけるＨＬＢは、有機概念図における有機性値（Ｏ）と無機性値（Ｉ）から、下記式（１）により算出された値である。
ＨＬＢ＝（Ｉ）／（Ｏ）×１０・・・（１）
ここで、（Ｏ）および（Ｉ）は、炭素１個を有機性値「２０」とし、その他の官能基については「有機概念図－基礎と応用－」（１９８４発行、甲田善生著、三共出版株式会社発行）の第１３頁に記載の無機性基表に従い算出した。また、同文献に記載のない官能基である－Ｏ－Ｐ（Ｏ）（ＯＨ）２については、同表に記載の＞Ｐ－の値を使用した。
<How to calculate HLB>
HLB in the present disclosure is a value calculated from the organic value (O) and inorganic value (I) in the organic conceptual diagram using the following formula (1).
HLB=(I)/(O)×10...(1)
Here, for (O) and (I), one carbon has an organic value of "20", and other functional groups are described in "Organic Concept Diagram - Basics and Applications" (published in 1984, written by Yoshio Koda, Sankyo Publishing). Calculation was made according to the inorganic base table described on page 13 of ``Published by Co., Ltd.''. Furthermore, for -OP(O)(OH) 2 , which is a functional group not described in the same document, the value of >P- described in the same table was used.
＜アニオン界面活性剤溶液の接触方法＞
イオン交換樹脂にアニオン界面活性剤を接触させる方法は特に限定はなく、接触工程１においてイオン交換樹脂にアルカリ成分を接触させる際の方法と同様の方法で行うことができる。アニオン界面活性剤溶液をカチオン交換樹脂と接触させることにより、アニオン界面活性剤溶液に含まれる陽イオン（金属イオン）を除去することができる。一方、アニオン界面活性剤溶液をアニオン交換樹脂と接触させることにより、アニオン界面活性剤溶液に含まれる陰イオン（ハロゲンイオン等）を除去することができる。カチオン交換樹脂とアニオン交換樹脂を用いた混床イオン交換法では、金属イオンと陰イオンを同時に除去することが可能である。
<Method of contacting anionic surfactant solution>
The method of bringing the anionic surfactant into contact with the ion exchange resin is not particularly limited, and can be carried out in the same manner as the method used in contacting the ion exchange resin with the alkali component in contact step 1. By bringing the anionic surfactant solution into contact with the cation exchange resin, cations (metal ions) contained in the anionic surfactant solution can be removed. On the other hand, by bringing the anionic surfactant solution into contact with an anion exchange resin, anions (halogen ions, etc.) contained in the anionic surfactant solution can be removed. In the mixed bed ion exchange method using a cation exchange resin and an anion exchange resin, it is possible to remove metal ions and anions at the same time.
以上説明した精製方法により、アニオン界面活性剤溶液中の金属イオンはカチオン成分と交換されるため、生成されたアニオン界面活性剤は中和塩の形をとる。そのため、酸型になると非水溶性となるアニオン界面活性剤を精製しても、アニオン界面活性剤の析出を防ぎ、アニオン界面活性剤中の金属イオンを効率よく低減することが可能となる。 By the purification method described above, the metal ions in the anionic surfactant solution are exchanged with cationic components, so the produced anionic surfactant takes the form of a neutralized salt. Therefore, even if the anionic surfactant, which becomes water-insoluble in the acid form, is purified, precipitation of the anionic surfactant can be prevented and metal ions in the anionic surfactant can be efficiently reduced.
以下、本開示の構成及び効果をより具体的とする実施例および比較例を挙げるが、本開示はこれらの実施例に限定されるものではない。以下の実施例及び比較例において、％は質量％を意味する。表１は、各実施例および各比較例におけるアニオン界面活性剤の種類及び濃度と、イオン交換樹脂にアルカリ成分を接触させる処理条件とを示す。なお、表１中のＨＬＢは、アニオン界面活性剤を酸型（酸成分）とした場合の有機概念図の計算式によるＨＬＢを示す。 Examples and comparative examples that make the configuration and effects of the present disclosure more specific are listed below, but the present disclosure is not limited to these examples. In the following examples and comparative examples, % means mass %. Table 1 shows the type and concentration of the anionic surfactant in each Example and each Comparative Example, and the treatment conditions for bringing the alkaline component into contact with the ion exchange resin. Note that HLB in Table 1 indicates the HLB based on the formula of the organic conceptual diagram when the anionic surfactant is in the acid type (acid component).
＜実施例１＞
アニオン界面活性剤としてラウリルリン酸モノエタノールアミン塩１７５ｇをイオン交換水４２５ｇと配合して、濃度２９．２％のアニオン界面活性剤溶液を調製し、これを試料とした。ラウリルリン酸モノエタノールアミン塩は、酸成分であるラウリルリン酸と対塩基であるモノエタノールアミンとの中和塩であり、ラウリルリン酸のＨＬＢは１１．２であった。強酸性カチオン交換樹脂として予め１Ｎ希塩酸を用いてＨ型に再生しておいたアンバーライト２００ＣＴ（米国デュポン社製の商品名）１００ｍｌを、垂直にセットした内容量３００ｍｌのカラムに充填した。充填した強酸性カチオン交換樹脂を、１０００ｇのイオン交換水にて十分に洗浄した後、２４時間静置した。強酸性カチオン交換樹脂に接触させるアルカリ成分としてモノエタノールアミン１５ｇをイオン交換水２３５ｇと配合して、アミン水溶液を調製した。調製したアミン水溶液及びカラム内の液温を１５～２５℃の範囲内で一定の温度に保ち、空間速度（ＳＶ）１．０ｈ－１でカラムに通液して、処理（接触工程１）を行った。処理した強酸性カチオン交換樹脂を、１０００ｇのイオン交換水にて十分に洗浄した。試料およびカラム内の液温を１５～２５℃の範囲内で一定の温度に保ち、空間速度（ＳＶ）１．０ｈ－１で試料をカラムに通液して、処理（接触工程２）を行った。これにより、試料をイオン交換法に供し、金属イオン濃度を低減した精製アニオン界面活性剤溶液を得た。
<Example 1>
As an anionic surfactant, 175 g of lauryl phosphate monoethanolamine salt was blended with 425 g of ion-exchanged water to prepare an anionic surfactant solution with a concentration of 29.2%, which was used as a sample. Lauryl phosphate monoethanolamine salt is a neutralized salt of lauryl phosphoric acid as an acid component and monoethanolamine as a counter base, and the HLB of lauryl phosphate was 11.2. 100 ml of Amberlite 200CT (trade name, manufactured by DuPont, USA), which had been previously regenerated into the H type using 1N dilute hydrochloric acid as a strongly acidic cation exchange resin, was packed into a vertically set column with an internal capacity of 300 ml. The filled strongly acidic cation exchange resin was thoroughly washed with 1000 g of ion exchange water, and then left to stand for 24 hours. An aqueous amine solution was prepared by blending 15 g of monoethanolamine with 235 g of ion-exchanged water as an alkaline component to be brought into contact with the strongly acidic cation exchange resin. The treatment (contact step 1) was carried out by keeping the prepared aqueous amine solution and the liquid temperature in the column at a constant temperature within the range of 15 to 25 °C, and passing the solution through the column at a space velocity (SV) of 1.0 h -1 . went. The treated strongly acidic cation exchange resin was thoroughly washed with 1000 g of ion exchange water. The sample and the liquid temperature in the column were kept constant within the range of 15 to 25°C, and the sample was passed through the column at a space velocity (SV) of 1.0 h -1 to perform the treatment (contact step 2). Ta. Thereby, the sample was subjected to an ion exchange method to obtain a purified anionic surfactant solution with reduced metal ion concentration.
＜実施例２＞
実施例１と同様にして、表１に記載したアニオン界面活性剤をイオン交換水に溶解したアニオン界面活性剤溶液を調製し、これを試料とした。強酸性カチオン交換樹脂として予め１Ｎ希塩酸を用いてＨ型に再生しておいたアンバーライト２００ＣＴ（米国デュポン社製の商品名）７５ｍｌと、強塩基性アニオン交換樹脂として予め１Ｎテトラメチルアンモニウム塩水溶液を用いてＯＨ型に再生しておいたアンバーライトＩＲＡ９００Ｊ（米国デュポン社製の商品名）７５ｍｌとを均一に混合した。当該混合樹脂を、垂直にセットした内容量３００ｍｌのカラムに充填した。充填した混合樹脂をイオン交換水にて十分に洗浄した後、２４時間静置した。強酸性カチオン交換樹脂に接触させるアルカリ成分としてモノエタノールアミンをイオン交換水と配合して、アミン水溶液を調製した。調製したアミン水溶液及びカラム内の液温を１５～２５℃の範囲内で一定の温度に保ち、空間速度（ＳＶ）０．８ｈ－１でカラムに通液して、処理（接触工程１）を行った。処理したイオン交換樹脂を、イオン交換水にて十分に洗浄した。試料およびカラム内の液温を１５～２５℃の範囲内で一定の温度に保ち、空間速度（ＳＶ）０．８ｈ－１で試料をカラムに通液して、処理（接触工程２）を行った。これにより、試料をイオン交換法に供し、金属イオン濃度を低減した精製アニオン界面活性剤溶液を得た。
<Example 2>
In the same manner as in Example 1, an anionic surfactant solution was prepared by dissolving the anionic surfactants listed in Table 1 in ion-exchanged water, and this was used as a sample. 75 ml of Amberlite 200CT (trade name, manufactured by DuPont, USA), which had been regenerated into H-form using 1N dilute hydrochloric acid as a strong acidic cation exchange resin, and 1N tetramethylammonium salt aqueous solution as a strong basic anion exchange resin. 75 ml of Amberlite IRA900J (trade name, manufactured by DuPont, USA), which had been used and regenerated into an OH type, was mixed uniformly. The mixed resin was packed into a vertically set column with an internal volume of 300 ml. After thoroughly washing the filled mixed resin with ion-exchanged water, it was allowed to stand for 24 hours. An aqueous amine solution was prepared by blending monoethanolamine with ion-exchanged water as an alkaline component to be brought into contact with a strongly acidic cation exchange resin. The treatment (contact step 1) was carried out by keeping the prepared aqueous amine solution and the liquid temperature in the column at a constant temperature within the range of 15 to 25 °C, and passing the solution through the column at a space velocity (SV) of 0.8 h -1 . went. The treated ion exchange resin was thoroughly washed with ion exchange water. The sample and the liquid temperature in the column were kept constant within the range of 15 to 25°C, and the sample was passed through the column at a space velocity (SV) of 0.8 h -1 to perform the treatment (contact step 2). Ta. Thereby, the sample was subjected to an ion exchange method to obtain a purified anionic surfactant solution with reduced metal ion concentration.
＜実施例３～９＞
実施例１と同様にして、表１に記載したアニオン界面活性剤をイオン交換水に溶解したアニオン界面活性剤溶液を調製して、試料とした。表１に示す強酸性カチオン交換樹脂に接触させるアルカリ成分の水溶液を調製し、カラムに充填したイオン交換樹脂に通液し、処理（接触工程１）を行った。表１に示す空間速度で試料をカラムに通液して、処理（接触工程２）を行った。これにより、試料をイオン交換法に供し、金属イオン濃度を低減した精製アニオン界面活性剤溶液を得た。
<Examples 3 to 9>
In the same manner as in Example 1, an anionic surfactant solution in which the anionic surfactants shown in Table 1 were dissolved in ion-exchanged water was prepared and used as a sample. An aqueous solution of an alkaline component to be brought into contact with the strongly acidic cation exchange resin shown in Table 1 was prepared, and the solution was passed through the ion exchange resin packed in a column to perform treatment (contact step 1). The sample was passed through the column at the space velocity shown in Table 1 to perform the treatment (contact step 2). Thereby, the sample was subjected to an ion exchange method to obtain a purified anionic surfactant solution with reduced metal ion concentration.
＜比較例１～３＞
比較例１では、強酸性カチオン交換樹脂に塩基を接触させる処理（接触工程１）を行わなかったこと以外は、実施例１と同様に行った。比較例２では、強酸性カチオン交換樹脂を用いず、強塩基性アニオン交換樹脂のみによって、表１に示す空間速度で処理を行ったこと以外は、実施例２と同様に行った。比較例３では、実施例１と同じアニオン界面活性剤溶液を調製し、その後の精製処理を行わなかった。
<Comparative Examples 1 to 3>
Comparative Example 1 was carried out in the same manner as Example 1, except that the treatment of contacting the strongly acidic cation exchange resin with a base (contact step 1) was not performed. Comparative Example 2 was carried out in the same manner as in Example 2, except that the treatment was performed using only a strongly basic anion exchange resin without using a strongly acidic cation exchange resin at the space velocity shown in Table 1. In Comparative Example 3, the same anionic surfactant solution as in Example 1 was prepared, and the subsequent purification treatment was not performed.
表１において、各記号は以下の製品を示す。
ＣＡ：アンバーライト２００ＣＴ（強酸性カチオン交換樹脂、ゲル型、米国デュポン社製）
ＡＮ：アンバーライトＩＲＡ９００Ｊ（強塩基性アニオン交換樹脂、ゲル型、米国デュポン社製）
In Table 1, each symbol indicates the following product.
CA: Amberlite 200CT (strongly acidic cation exchange resin, gel type, manufactured by DuPont, USA)
AN: Amberlite IRA900J (strongly basic anion exchange resin, gel type, manufactured by DuPont, USA)
実施例１～９、比較例１～３で得られた精製アニオン界面活性剤溶液について、下記試験方法により、溶液における溶状（析出の有無等）と金属含有量とを評価・測定した。その結果を表２に示す。 Regarding the purified anionic surfactant solutions obtained in Examples 1 to 9 and Comparative Examples 1 to 3, the solubility (presence or absence of precipitation, etc.) and metal content in the solutions were evaluated and measured by the following test method. The results are shown in Table 2.
≪溶状の評価≫
精製アニオン界面活性剤溶液を目視で観察し、析出の有無等を評価した。
≪Evaluation of solution condition≫
The purified anionic surfactant solution was visually observed to evaluate the presence or absence of precipitation.
≪金属含有量≫
精製アニオン界面活性剤溶液を、ファーネス原子吸光光度計ＡＡ２８０Ｚ（アジレント・テクノロジー社製の商品名）を用いたグラファイトファーネス式フレームレス原子化法による原子吸光分析法に供して、金属含有量を測定した。
The purified anionic surfactant solution was subjected to atomic absorption spectrometry using a graphite furnace flameless atomization method using a furnace atomic absorption spectrophotometer AA280Z (trade name manufactured by Agilent Technologies) to measure the metal content. .
実施例１から９は、精製アニオン界面活性剤溶液の溶状は液状であり、析出は無かった。また、実施例１から９では、精製後の各金属含有量は各金属イオンにおいて１００ｐｐｂ以下に低減されていた。一方、比較例１では、イオン交換樹脂にアルカリ成分を接触させる接触工程１を行わなかったため、精製途中で析出があった。比較例２では、接触工程１においてカチオン交換樹脂を用いずアニオン交換樹脂のみで処理したため、金属含有量が各金属イオンにおいて９０～４９００ｐｐｂもあった。また、イオン交換処理を行っていない比較例３では、金属含有量が各金属イオンにおいて１００～５０００ｐｐｂもあった。 In Examples 1 to 9, the solution state of the purified anionic surfactant solution was liquid, and there was no precipitation. Further, in Examples 1 to 9, the content of each metal after purification was reduced to 100 ppb or less for each metal ion. On the other hand, in Comparative Example 1, since the contact step 1 of bringing the alkali component into contact with the ion exchange resin was not performed, precipitation occurred during purification. In Comparative Example 2, the metal content was as high as 90 to 4900 ppb for each metal ion because the contact step 1 was treated with only an anion exchange resin without using a cation exchange resin. Furthermore, in Comparative Example 3 in which ion exchange treatment was not performed, the metal content was as high as 100 to 5000 ppb for each metal ion.
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| JP2002059160A (en) * | 2000-08-11 | 2002-02-26 | Daikin Ind Ltd | Separation method of fluorine-containg anionic surfactant |
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| JP2016019958A (en) * | 2014-07-16 | 2016-02-04 | 株式会社トクヤマ | Method for purifying nonionic surfactant |
| JP2016022473A (en) * | 2014-07-25 | 2016-02-08 | 竹本油脂株式会社 | Purification processing method of betaine type surfactant, and purified betaine type surfactant |
| JP2017132700A (en) * | 2016-01-26 | 2017-08-03 | 竹本油脂株式会社 | Method for treating nonionic type surfactant and method for producing nonionic type surfactant having reduced metal ion concentration |
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