JP7123463B1 - Method for purifying anionic surfactant - Google Patents
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- JP7123463B1 JP7123463B1 JP2022105689A JP2022105689A JP7123463B1 JP 7123463 B1 JP7123463 B1 JP 7123463B1 JP 2022105689 A JP2022105689 A JP 2022105689A JP 2022105689 A JP2022105689 A JP 2022105689A JP 7123463 B1 JP7123463 B1 JP 7123463B1
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- exchange resin
- anionic surfactant
- ion exchange
- acidic cation
- cation exchange
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- 239000003945 anionic surfactant Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 47
- 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 101
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 58
- 230000002378 acidificating effect Effects 0.000 claims abstract description 54
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 50
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 50
- 239000003957 anion exchange resin Substances 0.000 claims description 30
- 238000000746 purification Methods 0.000 claims description 19
- 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
- 239000002253 acid Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000013522 chelant Substances 0.000 claims description 8
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 7
- 229940023913 cation exchange resins Drugs 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 31
- 238000001556 precipitation Methods 0.000 abstract description 9
- 125000002091 cationic group Chemical group 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- -1 alkali metal salt Chemical class 0.000 description 13
- 238000005342 ion exchange Methods 0.000 description 12
- 229920001429 chelating resin Polymers 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- 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 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 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
- 239000003513 alkali Substances 0.000 description 5
- 239000002245 particle Substances 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
- 239000007864 aqueous solution Substances 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
- 150000001768 cations Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 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
- 230000000274 adsorptive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 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
- 238000001914 filtration 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
- 230000007257 malfunction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 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
- 229960004418 trolamine Drugs 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-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 class OCCNCCO.CCCCCCCCCCCC(O)=O MGDNLGRMXPBCOR-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 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
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003599 detergent Substances 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
- 238000005516 engineering process 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
- 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
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 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 compound 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
- 229920001495 poly(sodium acrylate) polymer Polymers 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
- BYKRNSHANADUFY-UHFFFAOYSA-M sodium octanoate Chemical compound [Na+].CCCCCCCC([O-])=O BYKRNSHANADUFY-UHFFFAOYSA-M 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
- 229940029614 triethanolamine stearate Drugs 0.000 description 1
- XFHHCPRMDXAWDO-UHFFFAOYSA-K trisodium;1-dodecoxydodecane;phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O.CCCCCCCCCCCCOCCCCCCCCCCCC XFHHCPRMDXAWDO-UHFFFAOYSA-K 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
【課題】アニオン界面活性剤について、処理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。【解決手段】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である。接触工程1では、アルカリ成分をイオン交換樹脂に接触させることにより、イオン交換樹脂に対してカチオン成分を吸着させる。接触工程2では、アニオン界面活性剤に含まれる金属イオンが、前記接触工程1でイオン交換樹脂に予め吸着されたカチオン成分と交換され、アニオン界面活性剤から金属イオンが除去される。【選択図】なしA method for purifying an anionic surfactant that efficiently reduces metal ions without causing precipitation during treatment is provided. A contacting step 1 of contacting an alkaline component with an ion exchange resin containing a strongly acidic cation exchange resin, and a contacting step 2 of contacting an anionic surfactant with the ion exchange resin obtained in the contacting step 1. A method for purifying an anionic surfactant, comprising: In the contacting step 1, the alkaline component is brought into contact with the ion exchange resin to adsorb the cationic component to the ion exchange resin. In the contacting step 2, the metal ions contained in the anionic surfactant are exchanged with the cationic components previously adsorbed on the ion exchange resin in the contacting step 1, and the metal ions are removed from the anionic surfactant. [Selection figure] None
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 methods 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 detergents containing surfactants are used in the technical fields of manufacturing devices such as electronic parts and semiconductors and precision processing. Contaminants and deposits that may be generated in the manufacturing process of silicon wafers, semiconductors, and the like include dirt and dust called particles, various metal ions, and the like. If there are particles on the semiconductor, it will cause a malfunction such as disconnection of the circuit. As a result, the semiconductor becomes unusable and the product yield decreases. Moreover, if metal ions are placed on the metal wiring of the semiconductor, current leakage may occur, causing the semiconductor to malfunction. The presence of metal ions can present significant problems for 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 been remarkably miniaturized, and the semiconductors used in these devices have also been miniaturized. Miniaturized semiconductors have narrower circuit line widths, and smaller particles can cause circuit deformation or the like, so particle removal with higher accuracy is required. Therefore, a highly purified surfactant with a reduced concentration of metal ions 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。 Conventional methods for purifying anionic surfactants include, in addition to general concentration, crystallization, and extraction methods, a method of filtration using an ultrafiltration membrane (see, for example, Patent Document 1), and an ion exchange membrane. A method of purifying by electrodialysis using (see, for example, 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。 Also known is a method of reducing the concentration of various metal ions by treating an alkali metal salt of an organic sulfonic acid with 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 an ion exchange membrane disclosed in Patent Document 1 or Patent Document 2, it is necessary to sufficiently reduce the metal ion concentration contained in the anionic surfactant solution. There is a problem that it is difficult to reduce the ion concentration to the level of several ppb for each metal ion.
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 state of metal salts or organic amine salts, but the solubility in water is significantly reduced in the acid-type state in which the hydrophilic group is combined with H + (proton). , becomes water-insoluble. When such an acid-type water-insoluble anionic surfactant is purified by the ion exchange method disclosed in Patent Document 3, an exchange reaction occurs between metal ions and H + of the strongly acidic cation exchange resin, and metal ions are reduced. Although it can be done, the anionic surfactant becomes an acid form and precipitates, making it impossible to purify.
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 an anionic surfactant that efficiently reduces metal ions 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 technique of the present disclosure takes the following means.
[1] A contacting step 1 of contacting an ion exchange resin containing a strongly acidic cation exchange resin with an alkaline component, and a contacting step 2 of contacting an anionic surfactant with the ion exchange resin obtained in the contacting 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] In the contacting step 1, after contacting an alkaline component with an ion exchange resin containing a strongly acidic cation exchange resin, 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 [1] to [4], wherein the anionic surfactant is a neutralized salt of an acid component with 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 addition, the numerical range indicated by "A to B" in this specification includes its upper limit and lower limit unless otherwise specified. That is, "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 the 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 by an ion exchange method. It includes a contacting step 1 of contacting an ion exchange resin containing a strongly acidic cation exchange resin with an alkaline component, and a contacting step 2 of contacting an anionic surfactant with the ion exchange resin obtained in the contacting 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>>
The contact step 1 is a step of contacting an ion exchange resin including a strongly acidic cation exchange resin with an alkaline component. By bringing the alkali component into contact with the ion exchange resin, the cation component derived from the alkali component can be adsorbed on the strongly acidic cation exchange resin contained in the ion exchange resin. Contacting step 1 may include step 1-1 described later.
<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 may contain a strongly acidic cation exchange resin, and may be composed of only the 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. Other ion exchange resins include weakly acidic cation exchange resins, strongly basic anion exchange resins, weakly basic anion exchange resins, chelate exchange resins, and the like. More than one species may be used in combination. 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 powdery, fibrous or filmy. The structure of the ion exchange resin may be gel type or 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 Impurity anions can also be reduced. Moreover, 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***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 having a relatively high adsorptive power for cationic components, and has a strongly acidic exchange group such as a sulfonic acid group (R — SO 3 −H + ) as a functional group. Examples of strongly acidic cation exchange resins include Amberlite (registered trademark, hereinafter the same) IR120B, IR124, 200CT (both manufactured by DuPont, USA), Duolite (registered trademark, hereinafter the same) C20, C21LF, C255LFH (both DuPont, USA). SK104H, SK110, SK1B (both manufactured by Mitsubishi Chemical Corporation) and the like 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***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 having relatively low adsorptive power for cationic components, and has weakly acidic exchange groups such as carboxylic acid groups (R—COO − H + ) as functional groups. Examples of weakly acidic cation exchange resins that can be used include Amberlite IRC76 and HPR8400 (both manufactured by DuPont, USA), Duolite C476 (both manufactured by DuPont, USA), and Diaion WK10 and WK11 (both manufactured by Mitsubishi Chemical).
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。 A strongly basic anion exchange resin is an anion exchange resin into which a strongly basic functional group such as a quaternary ammonium base (RN + R 1 R 2 R 3 ) is introduced. Examples of strongly basic anion exchange resins include Amberlite IRA400J, IRA402BL, and IRA900J (both manufactured by DuPont, USA), Duolite A113LF, A161JCL (both manufactured by DuPont, USA), and Diaion SA10A and SA11A (both manufactured by Mitsubishi Chemical Corporation). ) and other type I strongly basic anion exchange resins, Amberlite IRA410J, IRA910CT, HPR4010 (both manufactured by DuPont in the United States), Duolite A116, A162LF (both manufactured by DuPont in the United States), Diaion SA20A, SA20ALL (both manufactured by Mitsubishi Chemical A type II strongly basic anion exchange resin, such as those manufactured by Epson 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。 Weakly basic anion exchange resins are anion exchange resins into which weakly basic functional groups such as primary to tertiary amines have been introduced. Examples of weakly basic anion exchange resins include Amberlite IRA67, IRA96SB, IRA98 (both manufactured by DuPont, USA), Duolite A368MS, A378D, A375LF (both manufactured by DuPont, USA), Diaion WA10, WA20 (both manufactured by Mitsubishi Chemical company) etc. can be used.
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。 Examples of chelate resins that can be used include Amberlite IRC747UPS and IRC748 (both manufactured by DuPont, USA), Duolite C467 (both manufactured by DuPont, USA), and Diaion CR11 and CR20 (both manufactured by Mitsubishi Chemical).
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。 Strongly acidic cation exchange resins and weakly acidic cation exchange resins are preferably used after making the counterion H-type in advance using an acid such as hydrochloric acid or sulfuric acid, and thoroughly washing with ion-exchanged water, ultrapure water, or the like before use. . After the metal ions are adsorbed in the contact step 2 described later, the ion exchange resin is in the alkali metal type, but it can be regenerated into the H type by the same operation as described above and used.
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。 Strongly basic anion exchange resins and weakly basic anion exchange resins are used after making the counter ions into the OH type using a salt such as a tetramethylammonium salt aqueous solution in advance and washing thoroughly with ion-exchanged water, ultrapure water, etc. preferably. In addition, as in the case of the cation exchange resin, one regenerated to 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 alkali component to be brought into contact with the ion-exchange resin may be any known one, and examples thereof include organic amines such as monoethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, and triethylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and the like. tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethyl(2-hydroxyethyl)ammonium hydroxide and other quaternary ammonium salts; and ammonia. The alkali component is preferably an organic amine, a quaternary ammonium salt, or ammonia, more preferably an organic amine or ammonia, and still more preferably an organic amine, from the viewpoint of ion exchange capacity. These alkaline components may be used singly 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 contacting the alkaline component with the ion exchange resin in the contacting step 1 is not particularly limited, and may be a column method or a batch method. The column method is preferable from the viewpoint of work efficiency. When a strongly acidic cation exchange resin and another ion exchange resin are used in combination in a column method, either a multi-layer system or a mixed system can be used. Known devices 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 the alkaline component liquid is brought 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 preferred.
≪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。
<<Step 1-1>>
In step 1-1, after contacting an ion exchange resin containing a strongly acidic cation exchange resin with an alkaline component, a strongly basic anion exchange resin, a weakly basic anion exchange resin, a weakly acidic cation exchange resin, and a chelate exchange resin are further added. (that is, an ion-exchange resin not containing a strongly acidic cation-exchange resin) is mixed with the ion-exchange resin. The purpose of the contact step 1 is to bring the alkaline component into contact with the ion-exchange resin to adsorb the cation component derived from the alkaline component to the strongly acidic cation-exchange resin. Therefore, when a strongly acidic cation exchange resin and an ion exchange resin other than a strongly acidic cation exchange resin are used in combination, the ion exchange resin may be mixed before contact with the alkaline component, or may be strongly acidic as in step 1-1. After contacting the ion exchange resin, including the cation exchange resin, 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>>
The contacting step 2 is a step of contacting the ion exchange resin obtained in the contacting step 1 with an anionic surfactant. When the anionic surfactant solution is passed through the ion exchange resin contacted with the alkali component in the contacting step 1, metal ions in the solution are exchanged not with H 2 + but with cationic components. 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 causing 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 an 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 any known anionic surfactant may be used. From the viewpoint of the amount of metal ions contained in the anionic surfactant solution and the solubility in ion-exchanged water or the like, the anionic surfactant is preferably a neutralized salt with a counterbase.
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 as long as it is known. For example, organic amines such as monoethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine and 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 singly 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 a base include (1) lauryl phosphate monoethanolamine salt, polyoxyethylene (EO2) lauryl phosphate monoethanolamine salt, polyoxyethylene (EO4) lauryl ether Sodium phosphate, phosphates such as polyoxyethylene (EO3) alkyl (C12-15) ether ammonium phosphate, (2) alkyldiphenyl ether disulfonic acid triethanolamine salt, sodium alkylsulfonate, dodecylbenzenesulfonic acid triethanolate Organic sulfonates such as amine salts, (3) polyoxyethylene (EO3) tridecyl ether carboxylic acid monoethanolamine salts, carboxylates such as sodium octanoate, (4) lauric acid diethanolamine salts, palmitic acid monoethanolamine salts, fatty acid salts such as triethanolamine stearate, (5) styrene/maleic acid copolymer ammonium salt, diallylamine/maleic acid copolymer ammonium salt, sodium polyacrylate, sodium polymethacrylate, acrylic acid -sodium salt of methacrylic acid copolymer, sodium salt of isobutylene-maleic acid copolymer, sodium salt of methoxy PEG-grafted polymethacrylate, and the like. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
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, for example, from the viewpoint of water solubility, is preferably a neutralized salt of an acid component having an HLB of 20 or less according to the formula of the organic conceptual diagram, and an HLB of 15 or less. more preferred. The acid component of the anionic surfactant means an acid-type state in which the hydrophilic group of the anionic surfactant is combined with H 2 + .
<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 by the following formula (1) from the organic value (O) and the inorganic value (I) in the organic conceptual diagram.
HLB=(I)/(O)×10 (1)
Here, in (O) and (I), one carbon has an organic value of "20", and other functional groups are "organic conceptual diagram - basics and applications -" (published in 1984, by Yoshio Koda, Sankyo Publishing It was calculated according to the inorganic base table described on page 13 of "Published by Co., Ltd.". Moreover, 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 for bringing the anionic surfactant into contact with the ion exchange resin is not particularly limited, and the same method as the method for bringing the alkaline component into contact with the ion exchange resin in the contact step 1 can be used. By contacting the anionic surfactant solution with a 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 (such as halogen ions) contained in the anionic surfactant solution can be removed. A mixed bed ion exchange method using a cation exchange resin and an anion exchange resin can simultaneously remove metal ions and anions.
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。 Since the metal ions in the anionic surfactant solution are exchanged with cationic components by the purification method described above, 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, it is possible to prevent precipitation of the anionic surfactant and efficiently reduce metal ions in the anionic surfactant.
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 will be given below, but the present disclosure is not limited to these examples. In the following examples and comparative examples, % means % by 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. In addition, HLB in Table 1 indicates HLB according to the calculation formula of the organic conceptual diagram when the anionic surfactant is in the acid form (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 deionized 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 phosphate as an acid component and monoethanolamine as a counter base, and the HLB of lauryl phosphate was 11.2. As a strongly acidic cation exchange resin, 100 ml of Amberlite 200CT (manufactured by DuPont, USA), which had been regenerated to H type in advance using 1N diluted hydrochloric acid, was packed in a vertical 300 ml column. The filled strongly acidic cation exchange resin was thoroughly washed with 1000 g of ion-exchanged water, and then allowed 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 prepared amine aqueous solution and the temperature of the liquid in the column are kept constant within the range of 15 to 25° C., and the liquid is passed through the column at a space velocity (SV) of 1.0 h −1 to perform the treatment (contact step 1). gone. The treated strongly acidic cation exchange resin was thoroughly washed with 1000 g of ion-exchanged water. The sample and the liquid temperature in the column are kept constant within the range of 15 to 25° C., and the sample is passed through the column at a space velocity (SV) of 1.0 h −1 for treatment (contact step 2). rice field. As a result, the sample was subjected to an ion exchange method to obtain a purified anionic surfactant solution with a 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 deionized water, and this was used as a sample. 75 ml of Amberlite 200CT (manufactured by DuPont in the United States), which had been regenerated to H type in advance using 1N diluted hydrochloric acid as a strongly acidic cation exchange resin, and 1N tetramethylammonium salt aqueous solution as a strongly basic anion exchange resin in advance. 75 ml of Amberlite IRA900J (trade name of Dupont, USA) which had been regenerated to OH type using the above was uniformly mixed. The mixed resin was packed in a vertical 300 ml column. The filled mixed resin was thoroughly washed with ion-exchanged water and 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 the strongly acidic cation exchange resin. The prepared aqueous amine solution and the temperature of the liquid in the column are maintained at a constant temperature within the range of 15 to 25° C., and the liquid is passed through the column at a space velocity (SV) of 0.8 h −1 to perform the treatment (contact step 1). gone. The treated ion-exchange resin was thoroughly washed with ion-exchanged water. The sample and the liquid temperature in the column are kept constant within the range of 15 to 25° C., and the sample is passed through the column at a space velocity (SV) of 0.8 h −1 to perform treatment (contact step 2). rice field. As a result, the sample was subjected to an ion exchange method to obtain a purified anionic surfactant solution with a 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 was prepared by dissolving the anionic surfactants listed in Table 1 in ion-exchanged water 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 passed through the ion exchange resin packed in a column for treatment (contacting step 1). The sample was passed through the column at the space velocity shown in Table 1 to carry out treatment (contact step 2). As a result, the sample was subjected to an ion exchange method to obtain a purified anionic surfactant solution with a 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 in Example 1, except that the treatment of contacting the strongly acidic cation exchange resin with a base (contacting step 1) was not carried out. Comparative Example 2 was carried out in the same manner as in Example 2, except that the treatment was carried out at the space velocity shown in Table 1 using only the strongly basic anion exchange resin without using the strongly acidic cation exchange resin. In Comparative Example 3, the same anionic surfactant solution as in Example 1 was prepared without subsequent purification treatment.
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 products.
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。 For the purified anionic surfactant solutions obtained in Examples 1 to 9 and Comparative Examples 1 to 3, the state of solution (presence or absence of precipitation, etc.) and the metal content in the solution were evaluated and measured by the following test methods. Table 2 shows the results.
≪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 the state of solution≫
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 frameless atomization method using a furnace atomic absorption photometer 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 purified anionic surfactant solution was liquid, and no precipitation occurred. Moreover, 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 contacting step 1 of contacting the alkaline component with the ion exchange resin was not performed, precipitation occurred during the purification. In Comparative Example 2, the metal content was as high as 90 to 4900 ppb for each metal ion because the contacting step 1 did not use a cation exchange resin but only an anion exchange resin. In addition, in Comparative Example 3 in which no ion exchange treatment was performed, the metal content was as high as 100 to 5000 ppb for each metal ion.
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CN117299234A (en) * | 2023-11-28 | 2023-12-29 | 山东健奕宏生物制药有限公司 | Lactitol ion exchange system and method |
CN117299234B (en) * | 2023-11-28 | 2024-02-13 | 山东健奕宏生物制药有限公司 | Lactitol ion exchange system and method |
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